Equilibrium isotopic fractionation of copper during oxidation/reduction, aqueous complexation and ore-forming processes: Predictions from hybrid density functional theory

NASA Astrophysics Data System (ADS)

Sherman, David M.

2013-10-01

Copper exists as two isotopes: 65Cu (∼30.85%) and 63Cu (∼69.15%). The isotopic composition of copper in secondary minerals, surface waters and oxic groundwaters is 1-12‰ heavier than that of copper in primary sulfides. Changes in oxidation state and complexation should yield substantial isotopic fractionation between copper species but it is unclear to what extent the observed Cu isotopic variations reflect equilibrium fractionation. Here, I calculate the reduced partition function ratios for chalcopyrite (CuFeS2), cuprite (Cu2O), tenorite (CuO) and aqueous Cu+, Cu+2 complexes using periodic and molecular hybrid density functional theory to predict the equilibrium isotopic fractionation of Cu resulting from oxidation of Cu+ to Cu+2 and by complexation of dissolved Cu. Among the various copper(II) complexes in aqueous environments, there is a significant (1.3‰) range in the reduced partition function ratios. Oxidation and congruent dissolution of chalcopyrite (CuFeS2) to dissolved Cu+2 (as Cu(H2O)5+2) yields 65-63δ(Cu+2-CuFeS2) = 3.1‰ at 25 °C; however, chalcopyrite oxidation/dissolution is incongruent so that the observed isotopic fractionation will be less. Secondary precipitation of cuprite (Cu2O) would yield further enrichment of dissolved 65Cu since 65-63δ(Cu+2-Cu2O) is 1.2‰ at 25 °C. However, precipitation of tenorite (CuO) will favor the heavy isotope by +1.0‰ making dissolved Cu isotopically lighter. These are upper-limit estimates for equilibrium fractionation. Therefore, the extremely large (9‰) fractionations between dissolved Cu+2 (or Cu+2 minerals) and primary Cu+ sulfides observed in supergene environments must reflect Rayleigh (open-system) or kinetic fractionation. Finally the previously proposed (Asael et al., 2009) use of δ65Cu in chalcopyrite to estimate the oxidation state of fluids that transported Cu in stratiform sediment-hosted copper deposits is refined.

Molecular controls on Cu and Zn isotopic fractionation in Fe-Mn crusts

NASA Astrophysics Data System (ADS)

Little, S. H.; Sherman, D. M.; Vance, D.; Hein, J. R.

2014-06-01

The isotopic systems of the transition metals are increasingly being developed as oceanic tracers, due to their tendency to be fractionated by biological and/or redox-related processes. However, for many of these promising isotope systems the molecular level controls on their isotopic fractionations are only just beginning to be explored. Here we investigate the relative roles of abiotic and biotic fractionation processes in controlling modern seawater Cu and Zn isotopic compositions. Scavenging to Fe-Mn oxides represents the principal output for Cu and Zn to sediments deposited under normal marine (oxic) conditions. Using Fe-Mn crusts as an analogue for these dispersed phases, we investigate the phase association and crystal chemistry of Cu and Zn in such sediments. We present the results of an EXAFS study that demonstrate unequivocally that Cu and Zn are predominantly associated with the birnessite (δ-MnO2) phase in Fe-Mn crusts, as previously predicted from sequential leaching experiments (e.g., Koschinsky and Hein, 2003). The crystal chemistry of Cu and Zn in the crusts implies a reduction in coordination number in the sorbed phase relative to the free metal ion in seawater. Thus, theory would predict equilibrium fractionations that enrich the heavy isotope in the sorbed phase (e.g., Schauble, 2004). In natural samples, Fe-Mn crusts and nodules are indeed isotopically heavy in Zn isotopes (at ∼1‰) compared to deep seawater (at ∼0.5‰), consistent with the predicted direction of equilibrium isotopic fractionation based on our observations of the coordination environment of sorbed Zn. Further, ∼50% of inorganic Zn‧ is chloro-complexed (the other ∼50% is present as the free Zn2+ ion), and complexation by Cl- is also predicted to favour equilibrium partitioning of light Zn isotopes into the dissolved phase. The heavy Zn isotopic composition of Fe-Mn crusts and nodules relative to seawater can therefore be explained by an inorganic fractionation during uptake. However, Cu in Fe-Mn crusts is isotopically light (at ∼0.3 to 0.5‰) compared to the dissolved phase in seawater (at ∼0.9‰). We suggest that this is because dissolved Cu in the oceans is overwhelmingly complexed to strong organic ligands, which are better competitors for the heavy isotope.

Copper isotope signatures in modern marine sediments

NASA Astrophysics Data System (ADS)

Little, Susan H.; Vance, Derek; McManus, James; Severmann, Silke; Lyons, Timothy W.

2017-09-01

The development of metal stable isotopes as tools in paleoceanography requires a thorough understanding of their modern marine cycling. To date, no Cu isotope data has been published for modern sediments deposited under low oxygen conditions. We present data encompassing a broad spectrum of hydrographic and redox regimes, including continental margin and euxinic (sulphide-containing) settings. Taken together with previously published data from oxic settings, these data indicate that the modern oceanic sink for Cu has a surprisingly homogeneous isotopic composition of about +0.3‰ (δ65Cu, relative to NIST SRM976). We suggest that this signature reflects one of two specific water-column processes: (1) an equilibrium isotope fractionation between soluble, isotopically heavy, Cu complexed to strong organic ligands and an isotopically light pool sorbed to particles that deliver Cu to the sediment, or (2) an equilibrium isotope fractionation between the same isotopically heavy ligand-bound pool and the particle reactive free Cu2+ species, with the latter being scavenged by particulates and thereby delivered to the sediment. An output flux of about +0.3‰ into sediments is isotopically light relative to the known inputs to the ocean (at around +0.6‰) and the seawater value of +0.6 to +0.9‰, suggesting the presence of an as yet unidentified isotopically light source of Cu to the oceans. We hypothesize that this source may be hydrothermal, or may result from the partial dissolution of continentally derived particles.

Study of the dynamics of Zn, Fe, and Cu in the soil-plant system during leaf litter decomposition using isotopic compositions

NASA Astrophysics Data System (ADS)

Pichat, S.; Fekiacova, Z.

2013-12-01

Litter decomposition is a key process in the cycle of the elements in the soil-plant system. We have investigated the dynamics of three essential micronutrients (Zn, Fe, and Cu) in the vegetal cover, litter, organic horizons, and upper soil horizon (0-2 and 5-10 cm) using both element concentrations and isotopic compositions. The study was conducted on the O3HP (Oak Observatory at the Haute-Provence Observatory) experimental field site in southern France. O3HP is located far from pollution sources. It has been a fallow land for 70 years with the tree cover represented mainly by oak trees (Quercus pubescens). The soil is a thin layer of Calcisol developed under Mediterranean climate. The area has been subdivided in four zones as a function of plant cover. The results for two of these zones, dominated by respectively Poaceae and Genista hispanica, are reported here. We found that the concentrations of the three elements increase from the Ol to the Of horizon. Copper concentration in the Of horizon is close to that of the soil, whereas it is lower for Fe and Zn. For isotopic compositions, the behavior of the three elements is, however, different, which suggests different processes of redistribution for these elements. An enrichment in light Fe isotopes was observed from the Ol to the Of horizon, the latter having an isotopic composition similar to that of the soil. Zinc isotopic compositions are also similar in the Of horizon and the soil but they are isotopically heavier than in the Ol horizon. For Cu, the O horizons are isotopically heavier than the soil, with Of being the heaviest horizon. In addition, for Cu and Zn, the profiles in the O-horizons in the Poaceae-dominated and Genista hispanica-dominated areas are similar but their values are offset, suggesting an influence of the vegetal cover. The increase in concentration for Cu, Zn and Fe with age/depth in the O horizons is in agreement with what is commonly observed in litter-bag experiments, e.g. 1,2. Two mechanisms have been invoked to explain this phenomenon: 1) addition of metals by aerial dust and wet deposition or 2) absorption of metals from the soil by organisms that develop on the litter. Our vertical profiles of isotopic compositions in the O horizons show that the first hypothesis is unlikely. Instead, they suggest a downward transfer of isotopically light metals from the fresh litter to the base of the O horizon. In addition, the assumption of an upward transfer of isopically heavy Cu and Zn from the upper soil horizon to the Of horizon is needed to fully explain the profiles we observed. 1 Lomander and Johansson (2001) Water, Air, and Soil Pollut. 132, 165-184 2 Scheid et al. (2009) Eur. J. Soil Sci. 60, 613-621

Isotopic composition of zinc, copper, and iron in lunar samples

NASA Astrophysics Data System (ADS)

Moynier, F.; Albarède, F.; Herzog, G. F.

2006-12-01

We determined by ICP-MS the concentrations and isotopic ratios of Fe, Cu, and Zn in the Ti-rich lunar basalt 74275, in the lunar orange glass 74220, and in up to 10 lunar soils, namely, 14163, 15231, 64501, 66041, 68841, 69941, 70011, 72501, 75081, and 76501. Two analyses of zinc in lunar basalt 74275 give δ 66Zn = 0.17‰ and 0.75‰, values within the range of those measured in terrestrial basalts; copper in lunar basalt 74275 has δ 65Cu ˜ +1.4‰, which is isotopically heavier than values observed in terrestrial basalts. In the orange glass, we measured δ 56Fe = -0.24‰, δ 65Cu = -0.42‰, and δ 66Zn ˜ -3.6‰. These values of δ are more negative than those obtained for 74275 and for typical lunar basalts, but for Cu, comparable to those observed in terrestrial sulfides and meteorites. In lunar soils we found 0.11‰ ⩽ δ 56Fe ⩽ 0.51‰, 2.6‰ ⩽ δ 65Cu ⩽ 4.5‰, and 2.2‰ ⩽ δ 66Zn ⩽ 6.4‰. Insofar as we can generalize from a small sample set, S, Fe, Cu, Zn, and Cd show similar trends in isotopic fractionation on the Moon. Lunar basalts have nearly terrestrial isotopic ratios. Relative to the lunar basalt 74275, the pyroclastic glass 74220 is enriched in the lighter isotopes of Fe, Cu, and Zn, and the soils are enriched in the heavier isotopes of Fe, Cu, and Zn. The patterns in the basalts are likely inherited from the source material; the light-isotope enrichments seen in the orange glass originated during lava fountaining or, less probably, during partial condensation of vapor; and the heavy-isotope enrichments in the lunar soils were likely created by a combination of processes that included micrometeorite vaporization and sputtering. In the orange glass, the light-isotope enrichments (relative to lunar basalts) of Zn are larger than those of Cu. If these enrichments reflect accurately the isotopic composition of the gas, they suggest that Cu is more volatile than Zn in the liquid from which the gas derived. A simple model built on the known flux of micrometeorites to the lunar surface and a published estimate that micrometeorites generate 10 times their own mass of vapor, predicts heavy-isotope enrichments comparable to those observed in soils but only if the regolith gardening rate is set at about one twentieth of the generally accepted value of 1 cm/My. This discrepancy may reflect the difference in the time constants for micrometeorite milling and decimeter-scale gardening, or the importance of sputtering.

Zn isotopes in hydrothermal sulfides and their oxidation products along the south mid-Atlantic ridge: evidence of hydrothermal fluid deposition

NASA Astrophysics Data System (ADS)

Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Lei, Jijiang; Wang, Hao; Li, Zhenggang

2018-04-01

Significant Zn isotope fractionation occurs during seafloor hydrothermal activities. Therefore, exploring variations in Zn isotope composition affected by hydrothermal fluids and oxidative processes would help to better understand hydrothermal fluid cycling and sulfide deposition on mid-ocean ridges. In this paper, the Zn isotope compositions of different types of sulfides and their oxidation products obtained from hydrothermal fields on the South Mid-Atlantic Ridge (13-15°S) were analyzed using a Neptune plus MC-ICP-MS. The δ66Zn ratios range from -0.14‰ to +0.38‰, and the average δ66Zn ratio is +0.12±0.06‰ ( n=21, 2 SD) for all the studied sulfides and oxidation products. The Cu-rich sulfides have a slightly heavier Zn isotope composition (average δ66Zn=+0.19±0.07‰, n=6) than the Zn-rich sulfides (average δ66Zn=-0.02±0.06‰, n=5). The Zn isotope compositions of the oxidation products are similar to those of the Cu-rich sulfides, with an average δ66Zn ratio of 0.14±0.06‰ ( n=10, 2 SD). The Zn isotope compositions of all the samples are generally within the ranges of sulfides from hydrothermal fields on other mid-ocean ridges, such as the East Pacific Rise (9°N, 21°N) and the Trans-Atlantic Geotraverse. However, the average Zn isotope composition indicates the presence of significantly lighter Zn isotopes relative to those reported in the literature (average δ66Zn=+0.39‰). The significant enrichment of the Zn-rich sulfides with light Zn isotopes reveals that kinetic fractionation likely occurs during mineral deposition. Furthermore, the Zn isotope compositions of the sulfides and their oxidation products (average δ66Zn=+0.12‰) are significantly lighter than the average Zn isotope composition of the ocean (δ66Zn=+0.5‰), which could further constrain the modern Zn isotope cycle in the ocean by serving as a sink for light Zn isotopes.

New Insights from Zinc and Copper Isotopic Compositions into the Sources of Atmospheric Particulate Matter from Two Major European Cities.

PubMed

Gonzalez, R Ochoa; Strekopytov, S; Amato, F; Querol, X; Reche, C; Weiss, D

2016-09-20

This study reports spatial and temporal variability of Zn and Cu isotopes in atmospheric particulate matter (PM) collected in two major European cities with contrasting atmospheric pollution, Barcelona and London. We demonstrate that nontraditional stable isotopes identify source contributions of Zn and Cu and can play a major role in future air quality studies. In Barcelona, samples of fine PM were collected at street level at sites with variable traffic density. The isotopic signatures ranged between -0.13 ± 0.09 and -0.51 ± 0.05‰ for δ(66)ZnIRMM and between +0.04 ± 0.20 and +0.33 ± 0.15‰ for δ(65)CuAE633. Copper isotope signatures similar to those of Cu sulfides and Cu/Sb ratios within the range typically found in brake wear suggest that nonexhaust emissions from vehicles are dominant. Negative Zn isotopic signatures characteristic for gaseous emissions from smelting and combustion and large enrichments of Zn and Cd suggest contribution from metallurgical industries. In London, samples of coarse PM collected on the top of a building over 18 months display isotope signatures ranging between +0.03 ± 0.04 and +0.49 ± 0.02‰ for δ(66)ZnIRMM and between +0.37 ± 0.17 and +0.97 ± 0.21‰ for δ(65)CuAE633. Heavy Cu isotope signatures (up to +0.97 ± 0.21‰) and higher enrichments and Cu/Sb ratios during winter time indicate important contribution from fossil fuel combustion. The positive δ(66)ZnIRMM signatures are in good agreement with signatures characteristic for ore concentrates used for the production of tires and galvanized materials, suggesting nonexhaust emissions from vehicles as the main source of Zn pollution.

Copper isotope behavior during extreme magma differentiation and degassing: a case study on Laacher See phonolite tephra (East Eifel, Germany)

NASA Astrophysics Data System (ADS)

Huang, Jian; Liu, Sheng-Ao; Wörner, Gerhard; Yu, Huimin; Xiao, Yilin

2016-09-01

Copper (Cu) isotopic analyses were performed on a set of samples from the Laacher See tephra (LST) (Eifel, Germany) to investigate whether Cu isotopes are fractionated during extreme magma differentiation and degassing. The LST represents a continuous fractional crystallization series from parental basanite through mafic to highly differentiated phonolites. Samples analyzed here include phonolites of variable degrees of differentiation, phonolite-basanite hybrid rocks formed by mixing basanite and phonolite magmas, and basanite-derived mega-crystals (i.e., clinopyroxene, amphibole, phlogopite). In addition, we analyzed a series of mafic parental lavas from surrounding volcanic centers to constrain the Cu isotopic features of the Eifel mantle. Mafic phonolites show strong depletion in Cu compared to their parental basanites from ~50 to ~3 ppm, indicating sulfide fractionation during the basanite-to-phonolite differentiation. Mass balance calculations, based on the most Cu-rich hybrid rock (δ65Cu = -0.21 ‰, [Cu] = 46.2 ppm), show that the parental basanite magmas have δ65Cu of ca. -0.21 ‰, lighter than those of the mafic phonolites (~0.11 ‰). This suggests that sulfide fractionation preferentially removes the lighter Cu isotope (63Cu) in S-saturated magmas. By contrast, all phonolites have a limited range of Cu contents (1.1 to 4.0 ppm) with no systematic variations with S, suggesting that Cu is not controlled by sulfide fractionation during the evolution of mafic to highly differentiated phonolites. The identical δ65Cu values (0.11 ± 0.03 ‰, 2SD, n = 10) of the phonolites, irrespective of highly diverse composition and extents of differentiation, indicate that fractional crystallization of silicates (e.g., plagioclase, sanidine, amphibole, pyroxene, olivine), Fe-Ti-oxides and phosphate (e.g., apatite) generates insignificant Cu isotope fractionation. The lack of correlations between δ65Cu and volatile contents (e.g., S, Cl) in the LST sequence implies that volcanic degassing causes no detectable Cu isotope fractionation of igneous rocks. Eifel basalts and mega-crystals have variable δ65Cu (-0.18 to 0.21 ‰) that are uncorrelated to MgO and Cu, suggesting that such variations were not caused by differentiation but reflect the Cu isotopic heterogeneity of the Eifel mantle source due to metasomatism by fluids derived from hydrothermally altered oceanic lithosphere.

Copper isotope fractionation in acid mine drainage

USGS Publications Warehouse

Kimball, B.E.; Mathur, R.; Dohnalkova, A.C.; Wall, A.J.; Runkel, R.L.; Brantley, S.L.

2009-01-01

We measured the Cu isotopic composition of primary minerals and stream water affected by acid mine drainage in a mineralized watershed (Colorado, USA). The ??65Cu values (based on 65Cu/63Cu) of enargite (??65Cu = -0.01 ?? 0.10???; 2??) and chalcopyrite (??65Cu = 0.16 ?? 0.10???) are within the range of reported values for terrestrial primary Cu sulfides (-1??? < ??65Cu < 1???). These mineral samples show lower ??65Cu values than stream waters (1.38??? ??? ??65Cu ??? 1.69???). The average isotopic fractionation (??aq-min = ??65Cuaq - ??65Cumin, where the latter is measured on mineral samples from the field system), equals 1.43 ?? 0.14??? and 1.60 ?? 0.14??? for chalcopyrite and enargite, respectively. To interpret this field survey, we leached chalcopyrite and enargite in batch experiments and found that, as in the field, the leachate is enriched in 65Cu relative to chalcopyrite (1.37 ?? 0.14???) and enargite (0.98 ?? 0.14???) when microorganisms are absent. Leaching of minerals in the presence of Acidithiobacillus ferrooxidans results in smaller average fractionation in the opposite direction for chalcopyrite (??aq-mino = - 0.57 ?? 0.14 ???, where mino refers to the starting mineral) and no apparent fractionation for enargite (??aq-mino = 0.14 ?? 0.14 ???). Abiotic fractionation is attributed to preferential oxidation of 65Cu+ at the interface of the isotopically homogeneous mineral and the surface oxidized layer, followed by solubilization. When microorganisms are present, the abiotic fractionation is most likely not seen due to preferential association of 65Cuaq with A. ferrooxidans cells and related precipitates. In the biotic experiments, Cu was observed under TEM to occur in precipitates around bacteria and in intracellular polyphosphate granules. Thus, the values of ??65Cu in the field and laboratory systems are presumably determined by the balance of Cu released abiotically and Cu that interacts with cells and related precipitates. Such isotopic signatures resulting from Cu sulfide dissolution should be useful for acid mine drainage remediation and ore prospecting purposes. ?? 2008 Elsevier Ltd.

Investigation of Cu-, Zn- and Fe-containing human brain proteins using isotopic-enriched tracers by LA-ICP-MS and MALDI-FT-ICR-MS

NASA Astrophysics Data System (ADS)

Becker, J. Susanne; Zoriy, Miroslav; Pickhardt, Carola; Przybylski, Michael; Becker, J. Sabine

2005-04-01

Identification of metal-containing proteins and determination of Cu, Fe, Zn concentration in very small protein volumes is of increasing importance in protein research. Proteins containing metal ions were analyzed directly and simultaneously in separated protein spots in two-dimensional gels (2D gels) by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as an element mass spectrometric technique. In order to study the formation of proteins containing Cu, Zn and Fe in a human brain sample, isotopic-enriched tracers (54Fe, 65Cu and 67Zn) were doped to two-dimensional gels of separated Alzheimer-diseased brain proteins after two-dimensional (2D) gel electrophoresis. The protein spots were screened systematically by LA-ICP-MS with respect to these metal ion intensities. 54Fe/56Fe, 65Cu/63Cu and 67Zn/64Zn isotope ratios in metal-containing proteins were measured directly by LA-ICP-MS. The isotope ratio measurements obtained by LA-ICP-MS indicate certain protein spots with a natural isotope composition of Cu, Zn and/or Fe. These proteins already contained the metal investigated in the original proteins and are stable enough to survive the reducing conditions during gel electrophoresis. On the other hand, proteins with a changed isotope ratio of metals in comparison to the isotope ratio in nature demonstrate the accumulation of tracers within the protein complexes during the tracer experiments in 2D gels. The identification of singular protein spots from Alzheimer-diseased brain separated by 2D gel electrophoresis was attempted by biopolymer mass spectrometry using MALDI-FTICR-MS after excision from the 2D gel and tryptic digestion.

Matrix and energy effects during in-situ determination of Cu isotope ratios by ultraviolet-femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Lazarov, Marina; Horn, Ingo

2015-09-01

Copper isotope compositions in Cu-bearing metals and minerals have been measured by deep (194 nm) ultraviolet femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry (UV-fsLA-MC-ICP-MS). Pure Cu-metal, brass, and several Cu-rich minerals (chalcopyrite, enargite, covellite, malachite and cuprite) have been investigated. A long-term reproducibility of better than 0.08‰ at the 95% confidence limit on the NIST SRM 976 (National Institute of Standards and Technology) Cu-metal standard has been achieved with this technique. The δ65Cu values for all samples have been calculated by standard-sample-standard bracketing with NIST SRM 976. All analyses have been carried out using Ni as a mass discrimination monitor added by nebulization prior to entering the plasma torch. For further verification samples have been analysed by conventional solution nebulization MC-ICP-MS and the results obtained have been compared with those from UV-fsLA-MC-ICP-MS. Several potential matrix-induced molecular interferences on the mineral copper isotope ratio, such as (32S33S)+ and (32S-16O17O)+ do not affect the Cu isotope measurements on sulfides, while hydrides, such as Zn-H or doubly-charged Sn2 + that interfere Ni isotopes can be either neglected or stripped by calculation. Matrix independent Cu-isotope measurements are sensitive to the energy density (fluence) applied onto the sample and can produce artificial shifts in the obtained δ65Cu values which are on the order of 3‰ for Cu-metal, 0.5‰ for brass and 0.3‰ for malachite when using energy density of up to 2 J/cm2 for ablation. A positive correlation between applied energy density and the magnitude of the isotope ratio shift has been found in the energy density range from 0.2 to 1.3 J/cm2 which is below the ablation threshold for ns-laser ablation. The results demonstrate that by using appropriate low fluence it is possible to measure Cu isotopic ratios in native copper and Cu-bearing sulfides, carbonates and oxides in situ with a precision of better than 0.1‰ (2SD) without using a matrix-matched standard during laser ablation analyses. Thus, this is a suitable tool to resolve Cu isotopic zoning larger than 0.1‰ in Cu-sulfides, carbonates and oxides.

Pb isotopic constraints on the formation of the Dikulushi Cu-Pb-Zn-Ag mineralisation, Kundelungu Plateau (Democratic Republic of Congo)

NASA Astrophysics Data System (ADS)

Haest, Maarten; Schneider, Jens; Cloquet, Christophe; Latruwe, Kris; Vanhaecke, Frank; Muchez, Philippe

2010-04-01

Base metal-Ag mineralisation at Dikulushi and in other deposits on the Kundelungu Plateau (Democratic Republic of Congo) developed during two episodes. Subeconomic Cu-Pb-Zn-Fe polysulphide ores were generated during the Lufilian Orogeny (c. 520 Ma ago) in a set of E-W- and NE-SW-oriented faults. Their lead has a relatively unradiogenic and internally inhomogeneous isotopic composition (206Pb/204Pb = 18.07-18.49), most likely generated by mixing of Pb from isotopically heterogeneous clastic sources. These sulphides were remobilised and enriched after the Lufilian Orogeny, along reactivated and newly formed NE-SW-oriented faults into a chalcocite-dominated Cu-Ag mineralisation of high economic interest. The chalcocite samples contain only trace amounts of lead and show mostly radiogenic Pb isotope signatures that fall along a linear trend in the 207Pb/204Pb vs. 206Pb/204Pb diagram (206Pb/204Pb = 18.66-23.65; 207Pb/204Pb = 15.72-16.02). These anomalous characteristics reflect a two-stage evolution involving admixture of both radiogenic lead and uranium during a young fluid event possibly c. 100 Ma ago. The Pb isotope systematics of local host rocks to mineralisation also indicate some comparable young disturbance of their U-Th-Pb systems, related to the same event. They could have provided Pb with sufficiently radiogenic compositions that was added to less radiogenic Pb remobilised from precursor Cu-Pb-Zn-Fe polysulphides, whereas the U most likely originated from external sources. Local metal sources are also suggested by the 208Pb/204Pb-206Pb/204Pb systematics of combined ore and rock lead, which indicate a pronounced and diversified lithological control of the immediate host rocks on the chalcocite-dominated Cu-Ag ores. The Pb isotope systematics of polysulphide mineralisation on the Kundelungu Plateau clearly record a diachronous evolution.

Preliminary study on copper isotopes of the Zijinshan ore field, Fujian Province, SE China

NASA Astrophysics Data System (ADS)

Zhao, Hai-Xiang

2017-04-01

Zijinshan Cu-Au polymetallic ore field is located in Southeast China, tectonically belonging to the Interior Cathaysia Block. It is a complete porphyry-epithermal mineralization system, including Luoboling porphyry Cu-Mo deposit, Zijinshan high sulfidation Cu-Au deposit, Yueyang low sulfidation Ag-Au deposit, Wuziqilong and Longjiangting transitional style Cu deposits, etc. Main ore minerals from Zijinshan and Wuziqilong deposits are covellite and digenite. Copper isotopic compositions of these two minerals were analyzed. Copper isotope ratios are reported in the standard delta notation: δ65 Cu‰¯[ (65Cu/63Cu)Sample/(65Cu/63Cu) ERM-AE633-1] ×1000. The overall δ65Cu values for the analysed samples vary from -2.76 to 1.33‰Ṫhe Zijinshan Cu-Au deposit show large Cu isotopic variability (-2.76 to 1.33), among which covellite samples range from -2.76‰ to 0.38‰ with -0.79‰ in average and digenite samples range from -1.8‰ to 1.33‰ with -0.11‰ in average. During the leaching process of hypogene sulphides, 65Cu was leached more easily and then trapped in the supergene enrichment zone. Therefore, enrichment minerals should be enriched in 65Cu and the leached cap enriched in 63Cu. Thus the relationship of δ65Cu values for different Cu reservoirs should be leached cap minerals < hypogene sulphides < enrichment minerals. Nonexistence of enriched δ65Cu values indicate that the major copper minerals (mainly covellite and digenite) in the Zijinshan Cu-Au deposit and Wuziqilong Cu deposit are of hypogene origin rather than secondary origin. At the Wuziqilong Cu deposit, Cu isotopes has narrow range from 0.16‰ to 0.43‰ with 0.31‰ in average, which is typically of hypogene origin. Two coexisting covellite -digenite fractionations (δ65Cu =δ65Cucovellite - δ65Cudigenite) are 0.27‰ and 0.18‰ relatively. For minerals of the Cu-S system, from chalcocite (Cu2S) to covellite (CuS), proportions of Cu(II) become higher and higher. The classical definition of the crystallographic structure of covellite indicated that one third of the Cu is Cu(II) and digenite (Cu1.8S) has one ninth of Cu(II). Therefore, covellite is more oxidized species and has higher δ65Cu compared with coexisting digenite.

An assessment of the accuracy of stable Fe isotope ratio measurements on samples with organic and inorganic matrices by high-resolution multicollector ICP-MS

NASA Astrophysics Data System (ADS)

Schoenberg, Ronny; von Blanckenburg, Friedhelm

2005-04-01

Multicollector ICP-MS-based stable isotope procedures provide the capability to determine small variations in metal isotope composition of materials, but they are prone to substantial bias introduced by inadequate sample preparation. Such a "cryptic" bias is not necessarily identifiable from the measured isotope ratios. The analytical protocol for Fe isotope analyses of organic and inorganic materials described here identifies and avoids such pitfalls. In medium-mass resolution mode of the ThermoFinnigan Neptune MC-ICP-MS, a 1-ppm Fe solution with an uptake rate of 50-70 [mu]L min-1 yielded 3 × 10-11 A on 56Fe for the ThermoFinnigan stable introduction system and 1.2-1.8 × 10-10 A for the ESI Apex-Q uptake system. Sensitivity was increased again 3-5-fold when using Finnigan X-cones instead of the standard H-cones. The combination of the ESI Apex-Q apparatus and X-cones allowed the determination of the isotope composition on as little as 50 ng of Fe. Fe isotope compositions were corrected for mass bias with both the standard-sample bracketing (SSB) method, and by using the 65Cu/63Cu ratio of added synthetic copper (Cu-doping) as internal monitor of mass discrimination. Both methods provide identical results on high-purity Fe solutions of either synthetic or natural samples. We prefer the SSB method because of its shorter analysis time and more straightforward correction of instrumental mass bias compared to Cu-doping. Strong error correlations of the data are observed in three isotope diagrams. Thus, we suggest that the quality assessment in such diagrams should be performed with error ellipses rather than error bars. Reproducibility of [delta]56Fe, [delta]57Fe and [delta]58Fe values of natural samples alone is not a sufficient criterion for accuracy. A set of tests is lined out that identify cryptic matrix effects and ensure a reproducible level of quality control. Using these criteria and the SSB correction method, we determined the external reproducibilities for [delta]56Fe, [delta]57Fe and [delta]58Fe at the 95% confidence interval from 318 measurements of 95 natural samples to be 0.049, 0.071 and 0.28[per mille sign], respectively.

The preliminary result of the δ65Cu and δ34S values of major ore minerals in the Erdenetiin-Ovoo Cu-Mo porphyry deposit, Northern Mongolia

NASA Astrophysics Data System (ADS)

KIM, Y.; Lee, I.; Oyungerel, S.; Jargal, L.; Tsedenbal, T.; Ryu, J. S.

2016-12-01

The copper isotope (δ65Cu) and sulfur isotope (δ34S) compositions of major ore minerals from the Erdenetiin-Ovoo Cu-Mo porphyry deposit were measured to trace sources of copper and sulfur, and to evaluate the precipitation environment of ore minerals. The major ore minerals are pyrite, chalcopyrite, molybdenite and chalcocite developed in the QSP (Quartz-Sericite-Pyrite) alteration zone. The sulfide minerals such as sphalerite and covellite, and carbonate ore minerals like malachite, azurite are also identified. The copper isotope ratios (65Cu/63Cu) of copper ore minerals (chalcopyrite, chalcocite, malachite, azurite, covellite and chrysocolla) were analyzed by the MC-ICPMS in KBSI located in Ochang, South Korea. The measured δ65Cu values relative to NIST 976 range from -1.01 ‰ to 5.76 ‰. The average δ65Cu values of sulfide minerals such as chalcopyrite (1.03 ‰), chalcocite (0.62 ‰) and covellite (0.51 ‰) seem to be relatively lower than those of carbonate and silicate Cu minerals such as malachite (0.24 ‰), azurite (2.17 ‰) and chrysocolla (5.76 ‰). The sulfur isotope ratios (34S/32S) of major sulfide minerals were measured by EA-CF-IRMS (Elemental Analyzer - Continuous Flow - Isotope Ratio Mass Spectrometer) in NCIRF, Seoul National University. The average δ34SV-CDT value is -1.1 ‰ indicating the magmatic signature of sulfur. There is the difference of δ34S values between sulfide minerals. While the δ34S values of pyrite, chalcopyrite and molybdenite range from -0.9 to 0.8 ‰, the δ34S values of chalcocite range from -2.6 ‰ to -1.4 ‰. These lower values might be attributed to the sulfur isotope fractionation during its precipitation.

A drift correction optimization technique for the reduction of the inter-measurement dispersion of isotope ratios measured using a multi-collector plasma mass spectrometer

NASA Astrophysics Data System (ADS)

Doherty, W.; Lightfoot, P. C.; Ames, D. E.

2014-08-01

The effects of polynomial interpolation and internal standardization drift corrections on the inter-measurement dispersion (statistical) of isotope ratios measured with a multi-collector plasma mass spectrometer were investigated using the (analyte, internal standard) isotope systems of (Ni, Cu), (Cu, Ni), (Zn, Cu), (Zn, Ga), (Sm, Eu), (Hf, Re) and (Pb, Tl). The performance of five different correction factors was compared using a (statistical) range based merit function ωm which measures the accuracy and inter-measurement range of the instrument calibration. The frequency distribution of optimal correction factors over two hundred data sets uniformly favored three particular correction factors while the remaining two correction factors accounted for a small but still significant contribution to the reduction of the inter-measurement dispersion. Application of the merit function is demonstrated using the detection of Cu and Ni isotopic fractionation in laboratory and geologic-scale chemical reactor systems. Solvent extraction (diphenylthiocarbazone (Cu, Pb) and dimethylglyoxime (Ni) was used to either isotopically fractionate the metal during extraction using the method of competition or to isolate the Cu and Ni from the sample (sulfides and associated silicates). In the best case, differences in isotopic composition of ± 3 in the fifth significant figure could be routinely and reliably detected for Cu65/63 and Ni61/62. One of the internal standardization drift correction factors uses a least squares estimator to obtain a linear functional relationship between the measured analyte and internal standard isotope ratios. Graphical analysis demonstrates that the points on these graphs are defined by highly non-linear parametric curves and not two linearly correlated quantities which is the usual interpretation of these graphs. The success of this particular internal standardization correction factor was found in some cases to be due to a fortuitous, scale dependent, parametric curve effect.

Implications for behavior of volatile elements during impacts—Zinc and copper systematics in sediments from the Ries impact structure and central European tektites

NASA Astrophysics Data System (ADS)

Rodovská, Zuzana; Magna, TomáÅ.¡; Žák, Karel; Kato, Chizu; Savage, Paul S.; Moynier, Frédéric; Skála, Roman; Ježek, Josef

2017-10-01

Moldavites are tektites genetically related to the Ries impact structure, located in Central Europe, but the source materials and the processes related to the chemical fractionation of moldavites are not fully constrained. To further understand moldavite genesis, the Cu and Zn abundances and isotope compositions were measured in a suite of tektites from four different substrewn fields (South Bohemia, Moravia, Cheb Basin, Lusatia) and chemically diverse sediments from the surroundings of the Ries impact structure. Moldavites are slightly depleted in Zn ( 10-20%) and distinctly depleted in Cu (>90%) relative to supposed sedimentary precursors. Moreover, the moldavites show a wide range in δ66Zn values between 1.7 and 3.7‰ (relative to JMC 3-0749 Lyon) and δ65Cu values between 1.6 and 12.5‰ (relative to NIST SRM 976) and are thus enriched in heavy isotopes relative to their possible parent sedimentary sources (δ66Zn = -0.07 to +0.64‰; δ65Cu = -0.4 to +0.7‰). In particular, the Cheb Basin moldavites show some of the highest δ65Cu values (up to 12.5‰) ever observed in natural samples. The relative magnitude of isotope fractionation for Cu and Zn seen here is opposite to oxygen-poor environments such as the Moon where Zn is significantly more isotopically fractionated than Cu. One possibility is that monovalent Cu diffuses faster than divalent Zn in the reduced melt and diffusion will not affect the extent of Zn isotope fractionation. These observations imply that the capability of forming a redox environment may aid in volatilizing some elements, accompanied by isotope fractionation, during the impact process. The greater extent of elemental depletion, coupled with isotope fractionation of more refractory Cu relative to Zn, may also hinge on the presence of carbonyl species of transition metals and electromagnetic charge, which could exist in the impact-induced high-velocity jet of vapor and melts.

Copper isotope fractionation during its interaction with soil and aquatic microorganisms and metal oxy(hydr)oxides: Possible structural control

NASA Astrophysics Data System (ADS)

Pokrovsky, O. S.; Viers, J.; Emnova, E. E.; Kompantseva, E. I.; Freydier, R.

2008-04-01

This work is aimed at quantifying the main environmental factors controlling isotope fractionation of Cu during its adsorption from aqueous solutions onto common organic (bacteria, algae) and inorganic (oxy(hydr)oxide) surfaces. Adsorption of Cu on aerobic rhizospheric ( Pseudomonas aureofaciens CNMN PsB-03) and phototrophic aquatic ( Rhodobacter sp. f-7bl, Gloeocapsa sp. f-6gl) bacteria, uptake of Cu by marine ( Skeletonema costatum) and freshwater ( Navicula minima, Achnanthidium minutissimum and Melosira varians) diatoms, and Cu adsorption onto goethite (FeOOH) and gibbsite (AlOOH) were studied using a batch reaction as a function of pH, copper concentration in solution and time of exposure. Stable isotopes of copper in selected filtrates were measured using Neptune multicollector ICP-MS. Irreversible incorporation of Cu in cultured diatom cells at pH 7.5-8.0 did not produce any isotopic shift between the cell and solution (Δ 65/63Cu(solid-solution)) within ±0.2‰. Accordingly, no systematic variation was observed during Cu adsorption on anoxygenic phototrophic bacteria ( Rhodobacter sp.), cyanobacteria ( Gloeocapsa sp.) or soil aerobic exopolysaccharide (EPS)-producing bacteria ( P. aureofaciens) in circumneutral pH (4-6.5) and various exposure times (3 min to 48 h): Δ 65Cu(solid-solution) = 0.0 ± 0.4‰. In contrast, when Cu was adsorbed at pH 1.8-3.5 on the cell surface of soil the bacterium P. aureofacienshaving abundant or poor EPS depending on medium composition, yielded a significant enrichment of the cell surface in the light isotope (Δ 65Cu (solid-solution) = -1.2 ± 0.5‰). Inorganic reactions of Cu adsorption at pH 4-6 produced the opposite isotopic offset: enrichment of the oxy(hydr)oxide surface in the heavy isotope with Δ 65Cu(solid-solution) equals 1.0 ± 0.25‰ and 0.78 ± 0.2‰ for gibbsite and goethite, respectively. The last result corroborates the recent works of Mathur et al. [Mathur R., Ruiz J., Titley S., Liermann L., Buss H. and Brantley S. (2005) Cu isotopic fractionation in the supergene environment with and without bacteria. Geochim. Cosmochim. Acta69, 5233-5246] and Balistrieri et al. [Balistrieri L. S., Borrok D. M., Wanty R. B. and Ridley W. I. (2008) Fractionation of Cu and Zn isotopes during adsorption onto amorhous Fe(III) oxyhydroxide: experimental mixing of acid rock drainage and ambient river water. Geochim. Cosmochim. Acta72, 311-328] who reported heavy Cu isotope enrichment onto amorphous ferric oxyhydroxide and on metal hydroxide precipitates on the external membranes of Fe-oxidizing bacteria, respectively. Although measured isotopic fractionation does not correlate with the relative thermodynamic stability of surface complexes, it can be related to their structures as found with available EXAFS data. Indeed, strong, bidentate, inner-sphere complexes presented by tetrahedrally coordinated Cu on metal oxide surfaces are likely to result in enrichment of the heavy isotope on the surface compared to aqueous solution. The outer-sphere, monodentate complex, which is likely to form between Cu 2+ and surface phosphoryl groups of bacteria in acidic solutions, has a higher number of neighbors and longer bond distances compared to inner-sphere bidentate complexes with carboxyl groups formed on bacterial and diatom surfaces in circumneutral solutions. As a result, in acidic solution, light isotopes become more enriched on bacterial surfaces (as opposed to the surrounding aqueous medium) than they do in neutral solution. Overall, the results of the present study demonstrate important isotopic fractionation of copper in both organic and inorganic systems and provide a firm basis for using Cu isotopes for tracing metal transport in earth-surface aquatic systems. It follows that both adsorption on oxides in a wide range of pH values and adsorption on bacteria in acidic solutions are capable of producing a significant (up to 2.5-3‰ (±0.1-0.15‰)) isotopic offset. At the same time, Cu interaction with common soil and aquatic bacteria, as well as marine and freshwater diatoms, at 4 < pH < 8 yields an isotopic shift of only ±0.2-0.3‰, which is not related to Cu concentration in solution, surface loading, the duration of the experiment, or the type of aquatic microorganisms.

Natural variations of copper and sulfur stable isotopes in blood of hepatocellular carcinoma patients

NASA Astrophysics Data System (ADS)

Balter, Vincent; Nogueira da Costa, Andre; Paky Bondanese, Victor; Jaouen, Klervia; Lamboux, Aline; Sangrajrang, Suleeporn; Vincent, Nicolas; Fourel, François; Télouk, Philippe; Gigou, Michelle; Lécuyer, Christophe; Srivatanakul, Petcharin; Bréchot, Christian; Albarède, Francis; Hainaut, Pierre

2015-01-01

The widespread hypoxic conditions of the tumor microenvironment can impair the metabolism of bioessential elements such as copper and sulfur, notably by changing their redox state and, as a consequence, their ability to bind specific molecules. Because competing redox state is known to drive isotopic fractionation, we have used here the stable isotope compositions of copper (65Cu/63Cu) and sulfur (34S/32S) in the blood of patients with hepatocellular carcinoma (HCC) as a tool to explore the cancer-driven copper and sulfur imbalances. We report that copper is 63Cu-enriched by ∼0.4‰ and sulfur is 32S-enriched by ∼1.5‰ in the blood of patients compared with that of control subjects. As expected, HCC patients have more copper in red blood cells and serum compared with control subjects. However, the isotopic signature of this blood extra copper burden is not in favor of a dietary origin but rather suggests a reallocation in the body of copper bound to cysteine-rich proteins such as metallothioneins. The magnitude of the sulfur isotope effect is similar in red blood cells and serum of HCC patients, implying that sulfur fractionation is systemic. The 32S-enrichment of sulfur in the blood of HCC patients is compatible with the notion that sulfur partly originates from tumor-derived sulfides. The measurement of natural variations of stable isotope compositions, using techniques developed in the field of Earth sciences, can provide new means to detect and quantify cancer metabolic changes and provide insights into underlying mechanisms.

Petrogenesis of Late Jurassic granodiorites from Gutian, Fujian Province, South China: Implications for multiple magma sources and origin of porphyry Cu-Mo mineralization

NASA Astrophysics Data System (ADS)

Li, Bin; Jiang, Shao-Yong; Lu, An-Huai; Lai, Jian-Qing; Zhao, Kui-Dong; Yang, Tao

2016-11-01

The Gutian porphyry Cu-Mo deposit is a newly proved porphyry copper deposit in the coastal South China associated with granodioritic porphyries. In this study, zircon U-Pb ages and Hf isotope data, as well as geochemical and Sr-Nd-Pb-Re-Os isotopic compositions, are reported for these intrusions and minerals. Both zircon U-Pb and molybdenite Re-Os dating suggest that the Gutian granodiorite porphyries and related mineralization formed at 160 Ma. The Gutian granodiorites show a low-Mg adakitic geochemical affinity, with relatively high K2O but low Cr and Ni contents. These rocks have initial (87Sr/86Sr)i ratios of 0.7085 to 0.7097, negative εNd(t) values (- 12.5 to - 7.8), (206Pb/204Pb)t ratios of 18.048 to 18.241, (207Pb/204Pb)t ratios of 15.609 to 15.628, and (208Pb/204Pb)t ratios of 38.494 to 38.667. Zircons from the granodiorites have negative εHf(t) values of - 15.7 to - 8.5, which are close to those of Cathaysia crust-derived melts. Geochemical and Sr-Nd-Pb-Hf isotopic compositions suggest that they may be derived from Late Jurassic thickened juvenile lower crust. These lower crustal magma sources may not only contain pre-Proterozoic basement rocks, but also involve Triassic and Middle-Late Jurassic arc magmas within the lower crust, which were likely derived from an enriched mantle source associated with paleo-Pacific Plate subduction from the Middle to Late Jurassic. The Gutian ore-related granodiorites represent a new example for significant contributions of ancient subduction melts and enriched mantle-derived sources for porphyry-type magmatism and Cu-Mo mineralization, which occurred in response to an arc regime during the Middle to Late Jurassic in South China. Supplemental Table S2. Hf isotopic compositions of zircons from the studied rocks from the Gutian porphyry deposit in South China. Supplemental Table S3. Statistics for zircon U-Pb ages and Hf isotope compositions from Gutian granodiorites in South China Supplemental Table S4. Major element (wt.%) and trace element (ppm) concentrations of Gutian intrusions in Fujian Province, South China. Supplemental Table S5. Sr and Nd isotopic compositions of the studied rocks from the Gutian porphyry deposit in Fujian Province, South China. Supplemental Table S6. Pb isotopic compositions of the studied rocks from the Gutian porphyry deposit in South China. Supplemental Table S7. Re-Os isotopic compositions of molybdenite from the Gutian porphyry deposit in South China.

Steroid isotopic standards for gas chromatography-combustion isotope ratio mass spectrometry (GCC-IRMS).

PubMed

Zhang, Ying; Tobias, Herbert J; Brenna, J Thomas

2009-03-01

Carbon isotope ratio (CIR) analysis of urinary steroids using gas chromatography-combustion isotope ratio mass spectrometry (GCC-IRMS) is a recognized test to detect illicit doping with synthetic testosterone. There are currently no universally used steroid isotopic standards (SIS). We adapted a protocol to prepare isotopically uniform steroids for use as a calibrant in GCC-IRMS that can be analyzed under the same conditions as used for steroids extracted from urine. Two separate SIS containing a mixture of steroids were created and coded CU/USADA 33-1 and CU/USADA 34-1, containing acetates and native steroids, respectively. CU/USADA 33-1 contains 5alpha-androstan-3beta-ol acetate (5alpha-A-AC), 5alpha-androstan-3alpha-ol-17-one acetate (androsterone acetate, A-AC), 5beta-androstan-3alpha-ol-11, 17-dione acetate (11-ketoetiocholanolone acetate, 11k-AC) and 5alpha-cholestane (Cne). CU/USADA 34-1 contains 5beta-androstan-3alpha-ol-17-one (etiocholanolone, E), 5alpha-androstan-3alpha-ol-17-one (androsterone, A), and 5beta-pregnane-3alpha, 20alpha-diol (5betaP). Each mixture was prepared and dispensed into a set of about 100 ampoules using a protocol carefully designed to minimize isotopic fractionation and contamination. A natural gas reference material, NIST RM 8559, traceable to the international standard Vienna PeeDee Belemnite (VPDB) was used to calibrate the SIS. Absolute delta(13)C(VPDB) and Deltadelta(13)C(VPDB) values from randomly selected ampoules from both SIS indicate uniformity of steroid isotopic composition within measurement reproducibility, SD(delta(13)C)<0.2 per thousand. This procedure for creation of isotopic steroid mixtures results in consistent standards with isotope ratios traceable to the relevant international reference material.

Hydrogen-isotope permeation barrier

DOEpatents

Maroni, Victor A.; Van Deventer, Erven H.

1977-01-01

A composite including a plurality of metal layers has a Cu-Al-Fe bronze layer and at least one outer layer of a heat and corrosion resistant metal alloy. The bronze layer is ordinarily intermediate two outer layers of metal such as austenitic stainless steel, nickel alloys or alloys of the refractory metals. The composite provides a barrier to hydrogen isotopes, particularly tritium that can reduce permeation by at least about 30 fold and possibly more below permeation through equal thicknesses of the outer layer material.

Mo isotope fractionation during hydrothermal evolution of porphyry Cu systems

NASA Astrophysics Data System (ADS)

Shafiei, Behnam; Shamanian, GholamHossein; Mathur, Ryan; Mirnejad, Hassan

2015-03-01

We present Mo isotope compositions of molybdenite types from three successive stages of ore deposition in several porphyry copper deposits of the Kerman region, Iran. The data provide new insights into controlling processes on Mo isotope fractionation during the hydrothermal evolution of porphyry systems. The Mo isotope compositions of 27 molybdenite samples show wide variations in δ97Mo ranging from -0.37 to +0.92 ‰. The data reveal that molybdenites in the early and transitional stages of mineralization (preferentially 2H polytypes; δ97Mo mean = 0.35 ‰) have higher δ97Mo values than late stage (mainly 3R polytypes; δ97Mo mean = 0.02 ‰) molybdenites. This trend suggests that fractionation of Mo isotopes occurred in high-temperature stages of mineralization and that hydrothermal systems generally evolve towards precipitation of molybdenite with lower δ97Mo values. Taking into account the genetic models proposed for porphyry Cu deposits along with the temperature-dependent fractionation of Mo isotope ratios, it is proposed that large variations of Mo isotopes in the early and the transitional stages of ore deposition could be controlled by the separation of the immiscible ore-forming fluid phases with different density, pH, and ƒO2 properties (i.e., brine and vapor). The fractionation of Mo isotopes during fluid boiling and Rayleigh distillation processes likely dominates the Mo isotope budget of the remaining ore-forming fluids for the late stage of mineralization. The lower δ97Mo values in the late stage of mineralization can be explained by depletion of the late ore-forming hydrothermal solutions in 97Mo, as these fluids have moved to considerable distance from the source. Finally, the relationship observed between MoS2 polytypes (2H and 3R) and their Mo isotopic compositions can be explained by the molecular vibration theory, in which heavier isotopes are preferentially partitioned into denser primary 2H MoS2 crystals.

Determining Prehistoric Mining Practices in Southeastern Europe Using Copper Isotopes

NASA Astrophysics Data System (ADS)

Powell, Wayne; Mathur, Ryan; Bankoff, H. Arthur; Bulatović, Aleksandar; Filipović, Vojislav

2017-04-01

Copper was first smelted from malachite at 5000 BCE in Serbia. There the Eneolithic (Copper Age) began with the production of small jewelry pieces and progressed to the casting of massive copper tools near its end, approximately 2000 years later. However, copper metallurgy in southeastern Europe ceased or significantly decreased in the later third millennium, several centuries before the Bronze Age began. Whether this metallurgical hiatus was the result a cultural shift or depletion of natural resources remains an ongoing subject of debate. It has been speculated that the marked reduction in metal production at the Eneolithic-Bronze Age transition was due to the exhaustion of surficial weathered oxide ores and the technical inability to smelt the underlying sulfide minerals. The behavior of copper isotopes in near-surface environments allows us to differentiate highly weathered oxide ores that occur at Earth's surface from non-weathered sulfide ores that occur at greater depth. The oxidation of copper generates fluids and associated minerals that are enriched in the 65Cu isotope. Thus, oxidative weathering of sulfide ores leads to the development of three stratified isotopic reservoirs for copper: 1) oxides above the water table that are enriched in 65Cu; 2) residual weathered sulfides minerals at the water table that are depleted in 65Cu; and 3) non-fractionated, non-weathered sulfide ore below the water table. And so, the transformative shift to sulfide-based metallurgy will be delineated by a significant decrease in δ65Cu in copper artifacts corresponding to the first use of 65Cu-depleted residual ore. The degree of variability of primary ore composition from numerable ore deposits would likely result in the overlap of copper isotope composition between populations of artifacts. Therefore, shifts in the mean copper isotope values and associated standard deviations would best reflect changes in ores use. A baseline value of -0.2‰ ±0.5 (1) was determined from an average of 164 published measurements from chalcopyrite and bornite from 8 epithermal and massive sulfide deposits. Twenty-two (88%) of Eneolithic artifacts (n=25) have values greater than this, whereas eight (73%) of the Early Bronze age artifacts (n=11) yield compositions less than -0.2‰. The mean of Middle Bronze Age, Late Bronze Age and Early Iron Age (n=86) cluster near -0.2‰. This pattern is consistent with a progression to the mining of ore assemblages from increasing depths through prehistory. The shift from 65Cu-enriched to 65Cu-depleted copper in artifacts across the Eneolithic-Bronze Age boundary at 2500 BCE indicates that accessible near-surface oxide ore reserves were depleted after approximately two millennia of mining, and that the beginning of the Bronze Age in the Balkans corresponded to the acquisition of pyrotechnology which allowed for the extraction of metals from sulfide minerals and the resumption of copper mining activity in the region.

Multi isotopic characterization (Li-Cu-Zn-Pb) of waste waters pollution in a small watershed (Loire River basin, France)

NASA Astrophysics Data System (ADS)

Millot, R.; Desaulty, A. M.; Perret, S.; Bourrain, X.

2016-12-01

The goal of this study is to use multi-isotopic signature to track the pollution in surface waters, and to understand the complex processes causing the metals mobilization and transport in the environment. In the present study, we investigate waste water releases from a hospital water treatment plant and its potential impact in a small river basin near Orléans in France (Egoutier watershed: 15 km²and 5 km long). We decided to monitor this small watershed which is poorly urbanized in the Loire river basin. Its spring is located in a pristine area (forested area), while it is only impacted some kilometers further by the releases rich in metals coming from a hospital water treatment plant. A sampling of these liquid effluents as well as dissolved load and sediment from upstream to downstream was realized and their concentrations and isotopic data were determined. Isotopic ratios were measured using a MC-ICP-MS at BRGM, after a specific protocol of purification for each isotopic systematics. Lithium isotopic compositions are rather homogeneous in river waters along the main course of the stream. The waste water signal is very different from the natural background with significant heavy lithium contribution (high δ7Li). Lead isotopic compositions are rather homogenous in river waters and sediments with values close to geologic background. For Zn, the sediments with high concentrations and depleted isotopic compositions (low δ66Zn), typical of an anthropic pollution, are strongly impacted. The analyses of Cu isotopes in sediments show the impact of waster waters, but also isotopic fractionations due to redox processes in the watershed. To better understand these processes controlling the release of metals in water, sequential extractions on sediments are in progress under laboratory conditions and will provide important constraints for metal distribution in this river basin.

Fingerprinting two metal contaminants in streams with Cu isotopes near the Dexing Mine, China.

PubMed

Song, Shiming; Mathur, Ryan; Ruiz, Joaquin; Chen, Dandan; Allin, Nicholas; Guo, Kunyi; Kang, Wenkai

2016-02-15

Transition metal isotope signatures are becoming useful for fingerprinting sources in surface waters. This study explored the use of Cu isotope values to trace dissolved metal contaminants in stream water throughout a watershed affected by mining by-products of the Dexing Mine, the largest porphyry Cu operation in Asia. Cu isotope values of stream water were compared to potential mineral sources of Cu in the mining operation, and to proximity to the known Cu sources. The first mineral source, chalcopyrite, CuFeS2 has a 'tight' cluster of Cu isotope values (-0.15‰ to +1.65‰; +0.37 ± 0.6‰, 1σ, n=10), and the second mineral source, pyrite (FeS2), has a much larger range of Cu isotope values (-4‰ to +11.9‰; 2.7 ± 4.3‰, 1σ, n=16). Dissolved Cu isotope values of stream water indicated metal derived from either chalcopyrite or pyrite. Above known Cu mineralization, stream waters are approximately +1.5‰ greater than the average chalcopyrite and are interpreted as derived from weathering of chalcopyrite. In contrast, dissolved Cu isotope values in stream water emanating from tailings piles had Cu isotope values similar to or greater than pyrite (>+6‰, a common mineral in the tailings). These values are interpreted as sourced from the tailings, even in solutions that possess significantly lower concentrations of Cu (<0.05 ppm). Elevated Cu isotope values were also found in two soil and two tailings samples (δ(65)Cu ranging between +2 to +5‰). These data point to the mineral pyrite in tailings as the mineral source for the elevated Cu isotope values. Therefore, Cu isotope values of waters emanating from a clearly contaminated drainage possess different Cu isotope values, permitting the discrimination of Cu derived from chalcopyrite and pyrite in solution. Data demonstrate the utility of Cu isotopic values in waters, minerals, and soils to fingerprint metallic contamination for environmental problems. Copyright © 2015 Elsevier B.V. All rights reserved.

Copper isotope fractionation between aqueous compounds relevant to low temperature geochemistry and biology

NASA Astrophysics Data System (ADS)

Fujii, Toshiyuki; Moynier, Frédéric; Abe, Minori; Nemoto, Keisuke; Albarède, Francis

2013-06-01

Isotope fractionation between the common Cu species present in solution (Cu+, Cu2+, hydroxide, chloride, sulfide, carbonate, oxalate, and ascorbate) has been investigated using both ab initio methods and experimental solvent extraction techniques. In order to establish unambiguously the existence of equilibrium isotope fractionation (as opposed to kinetic isotope fractionation), we first performed laboratory-scale liquid-liquid distribution experiments. Upon exchange between HCl medium and a macrocyclic complex, the 65Cu/63Cu ratio fractionated by -1.06‰ to -0.39‰. The acidity dependence of the fractionation was appropriately explained by ligand exchange reactions between hydrated H2O and Cl- via intramolecular vibrations. The magnitude of the Cu isotope fractionation among important Cu ligands was also estimated by ab initio methods. The magnitude of the nuclear field shift effect to the Cu isotope fractionation represents only ˜3% of the mass-dependent fractionation. The theoretical estimation was expanded to chlorides, hydroxides, sulfides, sulfates, and carbonates under different conditions of pH. Copper isotope fractionation of up to 2‰ is expected for different forms of Cu present in seawater and for different sediments (carbonates, hydroxides, and sulfides). We found that Cu in dissolved carbonates and sulfates is isotopically much heavier (+0.6‰) than free Cu. Isotope fractionation of Cu in hydroxide is minimal. The relevance of these new results to the understanding of metabolic processes was also discussed. Copper is an essential element used by a large number of proteins for electron transfer. Further theoretical estimates of δ65Cu in hydrated Cu(I) and Cu(II) ions, Cu(II) ascorbates, and Cu(II) oxalate predict Cu isotope fractionation during the breakdown of ascorbate into oxalate and account for the isotopically heavy Cu found in animal kidneys.

Anhydrite pseudomorphs and the origin of stratiform Cu-Co ores in the Katangan Copperbelt (Democratic Republic of Congo)

NASA Astrophysics Data System (ADS)

Muchez, Ph.; Vanderhaeghen, P.; El Desouky, H.; Schneider, J.; Boyce, A.; Dewaele, S.; Cailteux, J.

2008-07-01

The stratiform Cu-Co ore mineralisation in the Katangan Copperbelt consists of dispersed sulphides and sulphides in nodules and lenses, which are often pseudomorphs after evaporites. Two types of pseudomorphs can be distinguished in the nodules and lenses. In type 1 examples, dolomite precipitated first and was subsequently replaced by Cu-Co sulphides and authigenic quartz, whereas in type 2 examples, authigenic quartz and Cu-Co sulphides precipitated prior to dolomite and are coarse-grained. The sulphur isotopic composition of the copper-cobalt sulphides in the type 1 pseudomorphs is between -10.3 and 3.1‰ relative to the Vienna Canyon Diablo Troilite, indicating that the sulphide component was derived from bacterial sulphate reduction (BSR). The generation of {text{HCO}}_3^ - during this process caused the precipitation and replacement of anhydrite by dolomite. A second product of BSR is the generation of H2S, resulting in the precipitation of Cu-Co sulphides from the mineralising fluids. Initial sulphide precipitation occurred along the rim of the pseudomorphs and continued towards the core. Precipitation of authigenic quartz was most likely induced by a pH decrease during sulphide precipitation. Fluid inclusion data from quartz indicate the presence of a high-salinity (8-18 eq. wt.% NaCl) fluid, possibly derived from evaporated seawater which migrated through the deep subsurface. 87Sr/86Sr ratios of dolomite in type 1 nodules range between 0.71012 and 0.73576, significantly more radiogenic than the strontium isotopic composition of Neoproterozoic marine carbonates (87Sr/86Sr = 0.7056-0.7087). This suggests intense interaction with siliciclastic sedimentary rocks and/or the granitic basement. The low carbon isotopic composition of the dolomite in the pseudomorphs (-7.02 and -9.93‰ relative to the Vienna Pee Dee Belemnite, V-PDB) compared to the host rock dolomite (-4.90 and +1.31‰ V-PDB) resulted from the oxidation of organic matter during BSR.

Hydrogen isotope trapping in Al-Cu binary alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chao, Paul; Karnesky, Richard A.

In this study, the trapping mechanisms for hydrogen isotopes in Al–X Cu (0.0 at. % < X < 3.5 at. %) alloys were investigated using thermal desorption spectroscopy (TDS), electrical conductivity, and differential scanning calorimetry. Constant heating rate TDS was used to determine microstructural trap energies and occupancies. In addition to the trapping states in pure Al reported in the literature (interstitial lattice sites, dislocations, and vacancies), a trap site due to Al–Cu intermetallic precipitates is observed. The binding energy of this precipitate trap is (18 ± 3) kJ•mol –1 (0.19 ± 0.03 eV). Typical occupancy of this trap ismore » high; for Al–2.6 at. % Cu (a Cu composition comparable to that in AA2219) charged at 200 °C with 130 MPa D 2 for 68 days, there is ca. there is 3.15×10 –7 mol D bound to the precipitate trap per mol of Al, accounting for a third of the D in the charged sample.« less

Hydrogen isotope trapping in Al-Cu binary alloys

DOE PAGES

Chao, Paul; Karnesky, Richard A.

2016-01-01

In this study, the trapping mechanisms for hydrogen isotopes in Al–X Cu (0.0 at. % < X < 3.5 at. %) alloys were investigated using thermal desorption spectroscopy (TDS), electrical conductivity, and differential scanning calorimetry. Constant heating rate TDS was used to determine microstructural trap energies and occupancies. In addition to the trapping states in pure Al reported in the literature (interstitial lattice sites, dislocations, and vacancies), a trap site due to Al–Cu intermetallic precipitates is observed. The binding energy of this precipitate trap is (18 ± 3) kJ•mol –1 (0.19 ± 0.03 eV). Typical occupancy of this trap ismore » high; for Al–2.6 at. % Cu (a Cu composition comparable to that in AA2219) charged at 200 °C with 130 MPa D 2 for 68 days, there is ca. there is 3.15×10 –7 mol D bound to the precipitate trap per mol of Al, accounting for a third of the D in the charged sample.« less

Thallium isotope variations in an ore-bearing continental igneous setting: Collahuasi Formation, northern Chile

NASA Astrophysics Data System (ADS)

Baker, R. G. A.; Rehkämper, M.; Ihlenfeld, C.; Oates, C. J.; Coggon, R.

2010-08-01

Thallium is a highly incompatible element and a large fraction of the bulk silicate Earth Tl budget is, therefore, expected to reside in the continental crust. Nonetheless, the Tl isotope systematics of continental rocks are essentially unexplored at present. Here, we present new Tl isotope composition and concentration data for a suite of 36 intrusive and extrusive igneous rocks from the vicinity of porphyry Cu deposits in the Collahuasi Formation of the Central Andes in northern Chile. The igneous lithologies of the rocks are variably affected by the hydrothermal alteration that accompanied the formation of the Cu deposits. The samples display Tl concentrations that vary by more than an order of magnitude, from 0.1 to 3.2 μg/g, whilst ɛ 205Tl ranges between -5.1 and +0.1 (ɛ 205Tl is the deviation of the 205Tl/ 203Tl isotope ratio of a sample from a standard in parts per 10 4). These variations are primarily thought to be a consequence of hydrothermal alteration processes, including metasomatic transport of Tl, and formation/breakdown of Tl-bearing minerals, which are associated with small but significant Tl isotope effects. The Tl abundances show excellent correlations with both K and Rb concentrations but no co-variation with Cu. This demonstrates that Tl displays only limited chalcophile affinity in the continental crust of the Collahuasi Formation, but behaves as a lithophile element with a distribution that is primarily governed by partitioning of Tl + into K +-bearing phases. Collahuasi samples with propylitic alteration features, which are derived from the marginal parts of the hydrothermal systems, have, on average, slightly lighter Tl isotope compositions than rocks from the more central sericitic and argillic alteration zones. This small but statistically significant difference most likely reflects preferential retention of isotopically heavy Tl in alteration phases, such as white micas and clays, which formed during sericitic and argillic alteration.

Zinc and copper behaviour at the soil-river interface: New insights by Zn and Cu isotopes in the organic-rich Rio Negro basin

NASA Astrophysics Data System (ADS)

Guinoiseau, Damien; Gélabert, Alexandre; Allard, Thierry; Louvat, Pascale; Moreira-Turcq, Patricia; Benedetti, Marc F.

2017-09-01

The complex behaviour of Zn and Cu at the soil-river interface was investigated in soil and riverine water samples from the Rio Negro basin, a secondary tributary of the Rio Amazonas, using their stable isotope compositions. This acidic and organic river drains two types of intensely weathered terrains: podzols in its upstream part, and lateritic soils downstream. Bulk soil particles, suspended particulate matter (SPM) as well as colloidal fractions were sampled across the whole basin during low and high water stages. In the basin, Zn and Cu are mostly exported from lateritic soils and transported by organic colloids where significant losses are observed in the downstream part of the river. The use of δ66Zn and δ65Cu measurements reveals distinct stories for these two metals in suspended sediments and colloids. In the colloids, the constant δ66Zncoll across the basin is induced by the same weak association mode between Zn and organic ligands, regardless of the origin of the water. By contrast, in SPM, the speciation of Zn and thus δ66ZnSPM differ according to the type of drained soils. Zn is associated with organic complexes in particles exported with water draining podzol whereas Zn2+ is incorporated in the structure of the remaining kaolinite clays in lateritic output. The stronger reactivity of Cu than Zn with organic ligands induces its complete complexation. Copper is controlled by refractory particulate organic matter (POM) and by reactive colloidal organic matter; the latter being enriched in 65Cu due to stronger binding interactions than in POM. While the Cu content remains constant in the upstream part of the Rio Negro, downstream, the decrease of SPM and colloidal Cu fluxes is associated with a constant δ65CuSPM and with an increase of δ65Cucoll at the Rio Negro outlet. Geochemical mass balance modelling, based on SPM, Cu and Zn fluxes in SPM and their associated isotopic signatures, confirms distinct host phases for Zn and Cu, and identifies the most probable places where losses of these two metals occur. In colloids, the observed Cu isotope fractionation (from 0.24 to 0.45‰) superimposed on the significant Cucoll loss is assumed to result from a new isotopic equilibrium in a low velocity and high productivity zone: Cu-rich colloids enriched in 63Cu aggregate and settle down, whereas the remaining heavy Cu is partially complexed on strong organic ligands secreted by phytoplankton, forming new Cu-colloids.

Evidence for a nonmagmatic component in potassic hydrothermal fluids of porphyry cu-Au-Mo systems, Yukon, Canada

NASA Astrophysics Data System (ADS)

Selby, David; Nesbitt, Bruce E.; Creaser, Robert A.; Reynolds, Peter H.; Muehlenbachs, Karlis

2001-02-01

Isotopic (H, Sr, Pb, Ar) and fluid inclusion data for hydrothermal fluids associated with potassic alteration from three Late Cretaceous porphyry Cu occurrences, west central Yukon, suggest a nonmagmatic fluid component was present in these hydrothermal fluids. Potassic stage quartz veins contain a dominant assemblage of saline and vapor-rich fluid inclusions that have δD values between -120 and -180‰. Phyllic stage quartz veins are dominated by vapor-rich fluid inclusions and have δD values that overlap with but are, on average, heavier (-117 to -132‰) than those in potassic stage quartz veins. These δD values are significantly lower than those from plutonic quartz phenocrysts (-91 to -113‰), and from values typically reported for primary fluids from porphyry-style mineralization (-40 to -100‰). The initial Sr ( 87Sr/ 86Sr i) isotopic values for the plutons are 0.7055 (Casino), 0.7048 (Mt. Nansen), and 0.7055 (Cash). The 87Sr/ 86Sr i compositions of hydrothermal K-feldspar ranges from magmatic Sr i values to more radiogenic compositions (Casino: 0.70551-0.70834, n = 8; Mt. Nansen: 0.7063-0.7070, n = 4; Cash: 0.7058, n = 1). The fluid inclusion waters from potassic quartz veins have 87Sr/ 86Sr i values that are similar to those of co-existing hydrothermal K-feldspar. The Pb isotopic compositions of hydrothermal K-feldspar show a weak positive correlation with Sr i for identical samples. Fluid inclusion waters of phyllic quartz veins also have Sr i compositions more radiogenic than the plutons. The Pb isotopic composition of pyrite and bornite from phyllic alteration veins are similar to, or more radiogenic than, hydrothermal K-feldspar Pb isotopic values. Hydrothermal K-feldspar samples yield 40Ar/ 39Ar ages (Casino = 71.9 ± 0.7 to 73.4 ± 0.8 Ma; Mt. Nansen = 68.2 ± 0.7 and 69.5 ± 0.6 Ma; Cash = 68.3 ± 0.8 Ma) similar to the U-Pb zircon, K-Ar biotite and Re-Os molybdenite ages of the Late Cretaceous plutons, with the age spectra indicating no excess 40Ar or disturbance. The 40Ar/ 36Ar values (285-292) of the K-feldspar samples are similar to the atmospheric compositions (295 ± 5) during Late Cretaceous time. The H, Sr, Pb, and Ar isotopic compositions of hydrothermal K-feldspar and quartz vein fluid inclusion waters that characterize the potassic hydrothermal fluids show evidence for an exotic component in addition to magmatic water (fluid). This component has a low δD, radiogenic Sr and Pb, and an atmospheric Ar composition. The inheritance of pre-existing isotope compositions from the host rocks, postpotassic alteration isotope exchange, or the replenishment of the magma chamber with magma of different isotopic composition cannot explain the isotope data. We suggest that to generate the observed H, Sr, Pb, and Ar isotope compositions, crustal fluids must be a component (15-94%) of potassic hydrothermal fluids in porphyry mineralization in the deposits studied.

Chemical vapor transport of chalcopyrite semiconductors: CuGaS2 and AgGaS2

NASA Astrophysics Data System (ADS)

Lauck, R.; Cardona, M.; Kremer, R. K.; Siegle, G.; Bhosale, J. S.; Ramdas, A. K.; Alawadhi, H.; Miotkowski, I.; Romero, A. H.; Muñoz, A.; Burger, A.

2014-09-01

Crystals of CuGaS2 and AgGaS2 with different isotopic compositions have been grown by chemical vapor transport (CVT) using iodine as the transport agent. Before performing the CVT growth, sulfur and copper were purified by sublimation and etching, respectively. 109Ag and the etched 71Ga isotopes were purified from oxides by vacuum annealing. Transparent yellow orange crystals of CuGaS2 and greenish yellow crystals of AgGaS2 were obtained in the shape of platelets, chunks, rods and needles in sizes of up to 8 mm (CuGaS2) and 30 mm (AgGaS2). These crystals were used to study their electronic, vibrational and thermodynamic properties. Higher excitonic states (n=2,3) were observed at low temperatures with wavelength-modulated reflectivity spectroscopy, thus proving an excellent surface and crystal quality. In addition, the experimentally determined non-monotonic temperature dependence of the excitonic energies can be well fitted by using two Bose-Einstein oscillators and their statistical factors, corresponding to characteristic acoustic and optical phonon frequencies. Isotopic shift of excitonic energies has also been successfully observed in these crystals.

Characteristics of Heavy Metals and Pb Isotopic Composition in Sediments Collected from the Tributaries in Three Gorges Reservoir, China

PubMed Central

Gao, Bo; Zhou, Huaidong; Huang, Yong; Wang, Yuchun; Gao, Jijun; Liu, Xiaobo

2014-01-01

The concentrations, distribution, accumulation, and potential ecological risk of heavy metals (Cr, Cu, Zn, Ni, As, Pb, Cd, and Hg) in sediments from the Three Gorges Reservoir (TGR) tributaries were determined and studied. Pb isotopic compositions in sediments were also measured to effectively identify the potential Pb sources. The results showed that the average concentrations of heavy metals in sediment of TGR tributaries were higher than the local background values of soils and sediments in China. The assessment by Geoaccumulation Index indicated that Cu, Ni, and Hg were at the “slightly polluted” level and Cd was ranked as the “moderately polluted” level in tributary sediments of TGR. The assessment by Potential Ecological Risk Index showed that Hg and Cd were the predominant elements in tributary sediments in TGR. The Pb isotopic ratios in sediments varied from 1.171 to 1.202 for 206Pb/207Pb and from 2.459 to 2.482 for 208Pb/207Pb in TGR. All Pb isotopic ratios in sediments were similar to those from coal combustion, lead ores (the mining activities and smelting process), and cement material, indicating that these anthropogenic inputs may be the main sources for Pb pollution in sediments of TGR tributaries. PMID:24624045

Voyager measurements of the isotopic composition of cosmic-ray aluminum and implications for the propagation of cosmic rays

NASA Technical Reports Server (NTRS)

Lukasiak, A.; Mcdonald, F. B.; Webber, W. R.

1994-01-01

We report a new measurement of the cosmic-ray isotopic composition of aluminum in the low-energy range form 75 to 206 MeV per nucleon.This measurement was made using the high-energy telescope of the CRS experiment on the Voyager 1 and 2 spacecraft during the time period from 1977 to 1993 with an average solar modulation level about 497 MV, roughly the same as at Earth near sunspot minimum. We obtain approximately 430 Al events of which approximately 35 are Al-26 and 395 are Al-27. The Al isotopes were separated with an average mass resolution sigma of 0.35 amu. Our interpretation of the isotopic composition of cosmic-ray aluminum is based on a standard Leaky-Box model for the interstellar propagation of cosmic-ray nuclei using the latest cross sections of the New Mexico-Saclay collaboration as well as a disk-halo diffusion model. From our observed ratio Al-26/Al-27 of 8.3 +/- 2.4 % we deduce an average interstellar density of about 0.52 (+0.26, -0.2) atoms per cu cm. This density is larger than the value of 0.28 (+0.14, -0.11) atoms per cu cm we found from an analysis of the observed abundance of the longer lived Be-10 made using data from the Voyager detectors over almost the same time interval and using essentially the same propagation program.

Eco-environmental implications of elemental and carbon isotope distributions in ornithogenic sediments from the Ross Sea region, Antarctica

NASA Astrophysics Data System (ADS)

Liu, Xiaodong; Nie, Yaguang; Sun, Liguang; Emslie, Steven D.

2013-09-01

Seabirds have substantial influence on geochemical circulation of elements, serving as a link for substance exchange between their foraging area and colonies. In this study, we investigated the elemental and carbon isotopic composition of five penguin-affected sediment profiles excavated from Ross Island and Beaufort Island in the Ross Sea region, Antarctica. Among the three main constituents of the sediments (including weathered bedrock, guano and algae), guano was the main source of organic matter and nutrients, causing selective enrichment of several elements in each of the sediment profiles. In the 22 measured elements, As, Cd, Cu, P, S, Se and Zn were identified as penguin bio-elements in the Ross Sea region through statistical analysis and comparison with local end-member environmental media such as weathered bedrock, fresh guano and fresh algae. Carbon isotopic composition in the ornithogenic sediments showed a mixing feature of guano and algae. Using a two-member isotope mixing equation, we were able to reconstruct the historical change of guano input and algal bio-mass. Compared with research in other parts of Antarctic, Arctic, and South China Sea, we found apparent overlap of avian bio-elements including As, Cd, Cu, P, Se, and Zn. Information on the composition and behavior of bio-elements in seabird guano on a global scale, and the role that bio-vectors play in the geochemical circulation between land and sea, will facilitate future research on avian ecology and paleoclimatic reconstruction.

Lead isotopic composition of trinitite melt glass: evidence for the presence of Canadian industrial lead in the first atomic weapon test.

PubMed

Bellucci, Jeremy J; Simonetti, Antonio; Wallace, Christine; Koeman, Elizabeth C; Burns, Peter C

2013-08-06

The Pb isotopic compositions for 51 spots of melt glass in 11 samples of trinitite have been determined by laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). Trinitite glass yields a large range of Pb isotopic compositions (i.e., (206)Pb/(204)Pb = 17.08-19.04), which reflect mixing between industrial Pb from materials used in the Trinity test and natural geologic components. Areas within trinitite melt glass containing high concentrations of both Cu and Pb, which are derived from the bomb and blast site-related components, were used for delineating the Pb isotopic composition corresponding to the anthropogenic Pb component. Comparison between the isotopic composition estimated here for the industrial Pb used in the Trinity test and those from known Pb deposits worldwide indicates close agreement with ore from the Buchans mine (Newfoundland, Canada). The Buchans mine was active during the time of the Trinity test and was operated by the American Smelting and Refining Company, which could have provided the Pb used in the test. The industrial Pb used in the Trinity test materials is not documented in the literature (or declassified) but could have been present in bricks, solder, pigs, or some other anthropogenic component related to the experiment.

Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water

USGS Publications Warehouse

Balistrieri, L.S.; Borrok, D.M.; Wanty, R.B.; Ridley, W.I.

2008-01-01

Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO3 electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu (65Cu/63Cu) and Zn (66Zn/64Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors (??soln-solid) are 0.99927 ?? 0.00008 for Cu and 0.99948 ?? 0.00004 for Zn or, alternately, the separation factors (??soln-solid) are -0.73 ?? 0.08??? for Cu and -0.52 ?? 0.04??? for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal-oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).

NanoSIMS Determination of Carbon and Oxygen Isotopic Compositions of Presolar Graphites from the Murchison Meteorite

NASA Technical Reports Server (NTRS)

Stadermann, F. J.; Croat, T. K.; Bernatowicz, T.

2004-01-01

Graphite from the Murchison density separate KFC1 (2.15 - 2.20 g/cu cm) has previously been studied by combined SEM/EDX and ion microprobe analysis. These studies found several distinct morphological types of graphites and C isotopic compositions that vary over more than 3 orders of magnitude, clearly establishing their presolar origin. Subsequent TEM measurements of a subset of these particles found abundant embedded crystals of metal (Zr, Mo, Ti, Ru) carbides which were incorporated during the growth of the graphites. A new TEM study of a large set of KFC1 graphites led to the discovery of another type of presolar material, Ru-Fe metal. Here we report results of the C and O isotopic measurements in the same graphite sections, which makes it possible for the first time to directly correlate isotopic and TEM data of KFC1 grains.

Isotopic variations of dissolved copper and zinc in stream waters affected by historical mining

USGS Publications Warehouse

Borrok, D.M.; Nimick, D.A.; Wanty, R.B.; Ridley, W.I.

2008-01-01

Zinc and Cu play important roles in the biogeochemistry of natural systems, and it is likely that these interactions result in mass-dependent fractionations of their stable isotopes. In this study, we examine the relative abundances of dissolved Zn and Cu isotopes in a variety of stream waters draining six historical mining districts located in the United States and Europe. Our goals were to (1) determine whether streams from different geologic settings have unique or similar Zn and Cu isotopic signatures and (2) to determine whether Zn and Cu isotopic signatures change in response to changes in dissolved metal concentrations over well-defined diel (24-h) cycles. Average ??66Zn and ??65Cu values for streams varied from +0.02??? to +0.46??? and -0.7??? to +1.4???, respectively, demonstrating that Zn and Cu isotopes are heterogeneous among the measured streams. Zinc or Cu isotopic changes were not detected within the resolution of our measurements over diel cycles for most streams. However, diel changes in Zn isotopes were recorded in one stream where the fluctuations of dissolved Zn were the largest. We calculate an apparent separation factor of ???0.3??? (66/64Zn) between the dissolved and solid Zn reservoirs in this stream with the solid taking up the lighter Zn isotope. The preference of the lighter isotope in the solid reservoir may reflect metabolic uptake of Zn by microorganisms. Additional field investigations must evaluate the contributions of soils, rocks, minerals, and anthropogenic components to Cu and Zn isotopic fluxes in natural waters. Moreover, rigorous experimental work is necessary to quantify fractionation factors for the biogeochemical reactions that are likely to impact Cu and Zn isotopes in hydrologic systems. This initial investigation of Cu and Zn isotopes in stream waters suggests that these isotopes may be powerful tools for probing biogeochemical processes in surface waters on a variety of temporal and spatial scales.

Heavy metals pollution and pb isotopic signatures in surface sediments collected from Bohai Bay, North China.

PubMed

Gao, Bo; Lu, Jin; Hao, Hong; Yin, Shuhua; Yu, Xiao; Wang, Qiwen; Sun, Ke

2014-01-01

To investigate the characteristics and potential sources of heavy metals pollution, surface sediments collected from Bohai Bay, North China, were analyzed for the selected metals (Cd, Cr, Cu, Ni, Pb, and Zn). The Geoaccumulation Index was used to assess the level of heavy metal pollution. Pb isotopic compositions in sediments were also measured to effectively identify the potential Pb sources. The results showed that the average concentrations of Cd, Cr, Cu, Ni, Pb, and Zn were 0.15, 79.73, 28.70, 36.56, 25.63, and 72.83 mg/kg, respectively. The mean concentrations of the studied metals were slightly higher than the background values. However, the heavy metals concentrations in surface sediments in Bohai Bay were below the other important bays or estuaries in China. The assessment by Geoaccumulation Index indicated that Cr, Zn, and Cd were classified as "the unpolluted" level, while Ni, Cu, and Pb were ranked as "unpolluted to moderately polluted" level. The order of pollution level of heavy metals was: Pb > Ni > Cu > Cr > Zn > Cd. The Pb isotopic ratios in surface sediments varied from 1.159 to 1.185 for (206)Pb/(207)Pb and from 2.456 to 2.482 for (208)Pb/(207)Pb. Compared with Pb isotopic radios in other sources, Pb contaminations in the surface sediments of Bohai Bay may be controlled by the mix process of coal combustion, aerosol particles deposition, and natural sources.

Influence of sulfur-bearing polyatomic species on high precision measurements of Cu isotopic composition

USGS Publications Warehouse

Pribil, M.J.; Wanty, R.B.; Ridley, W.I.; Borrok, D.M.

2010-01-01

An increased interest in high precision Cu isotope ratio measurements using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has developed recently for various natural geologic systems and environmental applications, these typically contain high concentrations of sulfur, particularly in the form of sulfate (SO42-) and sulfide (S). For example, Cu, Fe, and Zn concentrations in acid mine drainage (AMD) can range from 100??g/L to greater than 50mg/L with sulfur species concentrations reaching greater than 1000mg/L. Routine separation of Cu, Fe and Zn from AMD, Cu-sulfide minerals and other geological matrices usually incorporates single anion exchange resin column chromatography for metal separation. During chromatographic separation, variable breakthrough of SO42- during anion exchange resin column chromatography into the Cu fractions was observed as a function of the initial sulfur to Cu ratio, column properties, and the sample matrix. SO42- present in the Cu fraction can form a polyatomic 32S-14N-16O-1H species causing a direct mass interference with 63Cu and producing artificially light ??65Cu values. Here we report the extent of the mass interference caused by SO42- breakthrough when measuring ??65Cu on natural samples and NIST SRM 976 Cu isotope spiked with SO42- after both single anion column chromatography and double anion column chromatography. A set of five 100??g/L Cu SRM 976 samples spiked with 500mg/L SO42- resulted in an average ??65Cu of -3.50?????5.42??? following single anion column separation with variable SO42- breakthrough but an average concentration of 770??g/L. Following double anion column separation, the average SO42-concentration of 13??g/L resulted in better precision and accuracy for the measured ??65Cu value of 0.01?????0.02??? relative to the expected 0??? for SRM 976. We conclude that attention to SO42- breakthrough on sulfur-rich samples is necessary for accurate and precise measurements of ??65Cu and may require the use of a double ion exchange column procedure. ?? 2010.

Small changes in Cu redox state and speciation generate large isotope fractionation during adsorption and incorporation of Cu by a phototrophic biofilm

NASA Astrophysics Data System (ADS)

Coutaud, Margot; Méheut, Merlin; Glatzel, Pieter; Pokrovski, Gleb S.; Viers, Jérôme; Rols, Jean-Luc; Pokrovsky, Oleg S.

2018-01-01

Despite the importance of phototrophic biofilms in metal cycling in freshwater systems, metal isotope fractionation linked to metal adsorption and uptake by biofilm remains very poorly constrained. Here, copper isotope fractionation by a mature phototrophic biofilm during Cu surface adsorption and incorporation was studied in batch reactor (BR) and open drip flow reactor (DFR) systems at ambient conditions. X-ray Absorption Spectroscopy (both Near Edge Structure, XANES, and Extended Fine Structure, EXAFS) at Cu K-edge of the biofilm after its interaction with Cu in BR experiments allowed characterizing the molecular structure of assimilated Cu and quantifying the degree of CuII to CuI reduction linked to Cu assimilation. For both BR and DFR experiments, Cu adsorption caused enrichment in heavy isotope at the surface of the biofilm relative to the aqueous solution, with an apparent enrichment factor for the adsorption process, ε65Cuads, of +1.1 ± 0.3‰. In contrast, the isotope enrichment factor during copper incorporation into the biofilm (ε65Cuinc) was highly variable, ranging from -0.6 to +0.8‰. This variability of the ε65Cuinc value was likely controlled by Cu cellular uptake via different transport pathways resulting in contrasting fractionation. Specifically, the CuII storage induced enrichment in heavy isotope, whereas the toxicity response of the biofilm to Cu exposure resulted in reduction of CuII to CuI, thus yielding the biofilm enrichment in light isotope. EXAFS analyses suggested that a major part of the Cu assimilated by the biofilm is bound to 5.1 ± 0.3 oxygen or nitrogen atoms, with a small proportion of Cu linked to sulfur atoms (NS < 0.6) of sulfhydryl groups. XANES analyses showed that the proportion of CuIIvs CuI, compared to the initial CuII/CuI ratio, decreased by 14% after the first hour of reaction and by 6% after 96 h of reaction. The value of ε65Cuinc of the biofilm exhibited a similar trend over time of exposure. Our study demonstrates the complexity of biological processes associated with live phototrophic biofilms, which produce large and contrasting isotope fractionations following rather small Cu redox and speciation changes during uptake, storage or release of the metal, i.e., favoring heavy isotopes during complexation with carboxylate ligands and light isotopes during reduction of CuII-O/N to CuI-sulfhydryl moieties.

Evidence for the extraterrestrial origin of a natural quasicrystal.

PubMed

Bindi, Luca; Eiler, John M; Guan, Yunbin; Hollister, Lincoln S; MacPherson, Glenn; Steinhardt, Paul J; Yao, Nan

2012-01-31

We present evidence that a rock sample found in the Koryak Mountains in Russia and containing icosahedrite, an icosahedral quasicrystalline phase with composition Al(63)Cu(24)Fe(13), is part of a meteorite, likely formed in the early solar system about 4.5 Gya. The quasicrystal grains are intergrown with diopside, forsterite, stishovite, and additional metallic phases [khatyrkite (CuAl(2)), cupalite (CuAl), and β-phase (AlCuFe)]. This assemblage, in turn, is enclosed in a white rind consisting of diopside, hedenbergite, spinel (MgAl(2)O(4)), nepheline, and forsterite. Particularly notable is a grain of stishovite (from the interior), a tetragonal polymorph of silica that only occurs at ultrahigh pressures (≥ 10 Gpa), that contains an inclusion of quasicrystal. An extraterrestrial origin is inferred from secondary ion mass spectrometry (18)O/(16)O and (17)O/(16)O measurements of the pyroxene and olivine intergrown with the metal that show them to have isotopic compositions unlike any terrestrial minerals and instead overlap those of anhydrous phases in carbonaceous chondrite meteorites. The spinel from the white rind has an isotopic composition suggesting that it was part of a calcium-aluminum-rich inclusion similar to those found in CV3 chondrites. The mechanism that produced this exotic assemblage is not yet understood. The assemblage (metallic copper-aluminum alloy) is extremely reduced, and the close association of aluminum (high temperature refractory lithophile) with copper (low temperature chalcophile) is unexpected. Nevertheless, our evidence indicates that quasicrystals can form naturally under astrophysical conditions and remain stable over cosmic timescales, giving unique insights on their existence in nature and stability.

Geochemistry of CI chondrites: Major and trace elements, and Cu and Zn Isotopes

NASA Astrophysics Data System (ADS)

Barrat, J. A.; Zanda, B.; Moynier, F.; Bollinger, C.; Liorzou, C.; Bayon, G.

2012-04-01

In order to check the heterogeneity of the CI chondrites and determine the average composition of this group of meteorites, we analyzed a series of six large chips (weighing between 0.6 and 1.2 g) of Orgueil prepared from five different stones. In addition, one sample from each of Ivuna and Alais was analyzed. Although the sizes of the chips used in this study were “large”, our results show evidence for minor chemical heterogeneity in Orgueil, particularly for alkali elements and U. After removal of one outlier sample, the spread of the results is considerably reduced. For most of the 46 elements analyzed in this study, the average composition calculated for Orgueil is in very good agreement with previous CI estimates. This average, obtained with a “large” mass of samples, is analytically homogeneous and is suitable for normalization purposes. Finally, the Cu and Zn isotopic ratios are homogeneously distributed within the CI parent body with a spread of less than 100 ppm per atomic mass unit (amu).

High Precision Iron Isotope Compositions in Components From the Allende CV3 Meteorite by MC-ICP-MS

NASA Astrophysics Data System (ADS)

Mullane, E.; Russell, S. S.; Weiss, D.; Mason, T. F.; Gounelle, M.

2001-12-01

Four chondrules and one matrix sample of Allende were examined for Fe-isotope frac-tionation, using multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS). Iron is the most volatile major constituent of chondrules and a recent study [1] suggested that solar system Fe was initially isotopically homogeneous. Thus, any isotopic variation is likely due to mass fractionation during nebular process-ing. The chondrule samples were split. One portion was subject to a standard acid dis-solution whilst the other was polished, ena-bling textural and compositional characteri-zation. Fe, Cu and Zn are separated from the remaining matrix elements [2], removing potential interfering ions from the solution. 100 % elemental recovery (within error) is achieved, ensuring that chromatographic fractionation does not occur [2]. Hydrogen is bled into the collision cell, minimising Ar polyatomic species interferences. Typical precisions of 0.1‰ (2σ ) for 54Fe/56Fe ratios are achieved for 75 replicates. Instrumental mass bias is assessed using (1) sample-standard brack-eting and (2) doping with Cu. A variation of 0.8‰ /amu is observed, which is approximately 18 times the analyti-cal uncertainty at the 2σ level. Our high precision data show that: (1) Allende chondrules and matrix exhibit clear isotopic variation in iron. (2) δ 54Fe val-ues appear to be correlated to the bulk FeO content, with the more iron rich samples enriched in the lighter 54Fe isotope. (3) δ 54Fe values appear to be unre-lated to texture, and consequently to the temperature of chondrule formation. Bulk Fe-content may be a proxy for the amount of volatilisation experienced, and volatilisation of Fe in chondrule precursor material has resulted in a residue of the heavier Fe isotopes. Chondrules are known to have often experienced several heating events, and their texture primarily reflects the nature of the last event. Thus, the lack of correlation between the δ 54Fe value and chondrule texture suggests that Fe-isotope composi-tion was derived from chondrule precursor material. [1] Zhu et al. (2001) Nature 412, p.311 [2] Mullane et al. (2001) LPS XXXII, No.1545.

Copper and tin isotopic analysis of ancient bronzes for archaeological investigation: development and validation of a suitable analytical methodology.

PubMed

Balliana, Eleonora; Aramendía, Maite; Resano, Martin; Barbante, Carlo; Vanhaecke, Frank

2013-03-01

Although in many cases Pb isotopic analysis can be relied on for provenance determination of ancient bronzes, sometimes the use of "non-traditional" isotopic systems, such as those of Cu and Sn, is required. The work reported on in this paper aimed at revising the methodology for Cu and Sn isotope ratio measurements in archaeological bronzes via optimization of the analytical procedures in terms of sample pre-treatment, measurement protocol, precision, and analytical uncertainty. For Cu isotopic analysis, both Zn and Ni were investigated for their merit as internal standard (IS) relied on for mass bias correction. The use of Ni as IS seems to be the most robust approach as Ni is less prone to contamination, has a lower abundance in bronzes and an ionization potential similar to that of Cu, and provides slightly better reproducibility values when applied to NIST SRM 976 Cu isotopic reference material. The possibility of carrying out direct isotopic analysis without prior Cu isolation (with AG-MP-1 anion exchange resin) was investigated by analysis of CRM IARM 91D bronze reference material, synthetic solutions, and archaeological bronzes. Both procedures (Cu isolation/no Cu isolation) provide similar δ (65)Cu results with similar uncertainty budgets in all cases (±0.02-0.04 per mil in delta units, k = 2, n = 4). Direct isotopic analysis of Cu therefore seems feasible, without evidence of spectral interference or matrix-induced effect on the extent of mass bias. For Sn, a separation protocol relying on TRU-Spec anion exchange resin was optimized, providing a recovery close to 100 % without on-column fractionation. Cu was recovered quantitatively together with the bronze matrix with this isolation protocol. Isotopic analysis of this Cu fraction provides δ (65)Cu results similar to those obtained upon isolation using AG-MP-1 resin. This means that Cu and Sn isotopic analysis of bronze alloys can therefore be carried out after a single chromatographic separation using TRU-Spec resin. Tin isotopic analysis was performed relying on Sb as an internal standard used for mass bias correction. The reproducibility over a period of 1 month (n = 42) for the mass bias-corrected Sn isotope ratios is in the range of 0.06-0.16 per mil (2 s), for all the ratios monitored.

Origin of native copper in the Paraná volcanic province, Brazil, integrating Cu stable isotopes in a multi-analytical approach

NASA Astrophysics Data System (ADS)

Baggio, Sérgio Benjamin; Hartmann, Léo Afraneo; Lazarov, Marina; Massonne, Hans-Joachim; Opitz, Joachim; Theye, Thomas; Viefhaus, Tillmann

2018-03-01

Different hypotheses exist on the origin of native copper mineralization in the Paraná volcanic province that invoke magmatic, late magmatic, or hydrothermal events. The average copper content in the host basalts is 200 ppm. Native copper occurs as dendrites in cooling joints, fractures, and cavities within amygdaloidal crusts. Cuprite, tenorite, chrysocolla, malachite, and azurite occur in breccias at the top of the lava flows. Chemical analyses, X-ray diffraction, Raman spectrometry, electron microprobe analyses, LA-ICP-MS, and Cu isotope analyses were used to evaluate the origin of native copper in the volcanic province. Copper contents in magnetite of the host basalt are close to 1 wt.%, whereas clinopyroxene contains up to 0.04 wt.% Cu. Cretaceous hydrothermal alteration of magnetite and clinopyroxene released copper to generate hydrothermal copper mineralization. The isotopic composition of the native copper in the Paraná volcanic province varies from -0.9‰ in the southeastern portion (Rio Grande do Sul state) to 1.9‰ in the central portion (Paraná state) of the province. This study supports a hydrothermal origin followed by supergene enrichment for native copper in the Paraná volcanic province.

Evidence for the extraterrestrial origin of a natural quasicrystal

PubMed Central

Bindi, Luca; Eiler, John M.; Guan, Yunbin; Hollister, Lincoln S.; MacPherson, Glenn; Steinhardt, Paul J.; Yao, Nan

2012-01-01

We present evidence that a rock sample found in the Koryak Mountains in Russia and containing icosahedrite, an icosahedral quasicrystalline phase with composition Al63Cu24Fe13, is part of a meteorite, likely formed in the early solar system about 4.5 Gya. The quasicrystal grains are intergrown with diopside, forsterite, stishovite, and additional metallic phases [khatyrkite (CuAl2), cupalite (CuAl), and β-phase (AlCuFe)]. This assemblage, in turn, is enclosed in a white rind consisting of diopside, hedenbergite, spinel (MgAl2O4), nepheline, and forsterite. Particularly notable is a grain of stishovite (from the interior), a tetragonal polymorph of silica that only occurs at ultrahigh pressures (≥10 Gpa), that contains an inclusion of quasicrystal. An extraterrestrial origin is inferred from secondary ion mass spectrometry 18O/16O and 17O/16O measurements of the pyroxene and olivine intergrown with the metal that show them to have isotopic compositions unlike any terrestrial minerals and instead overlap those of anhydrous phases in carbonaceous chondrite meteorites. The spinel from the white rind has an isotopic composition suggesting that it was part of a calcium-aluminum-rich inclusion similar to those found in CV3 chondrites. The mechanism that produced this exotic assemblage is not yet understood. The assemblage (metallic copper-aluminum alloy) is extremely reduced, and the close association of aluminum (high temperature refractory lithophile) with copper (low temperature chalcophile) is unexpected. Nevertheless, our evidence indicates that quasicrystals can form naturally under astrophysical conditions and remain stable over cosmic timescales, giving unique insights on their existence in nature and stability. PMID:22215583

Intracellular Cadmium Isotope Fractionation

NASA Astrophysics Data System (ADS)

Horner, T. J.; Lee, R. B.; Henderson, G. M.; Rickaby, R. E.

2011-12-01

Recent stable isotope studies into the biological utilization of transition metals (e.g. Cu, Fe, Zn, Cd) suggest several stepwise cellular processes can fractionate isotopes in both culture and nature. However, the determination of fractionation factors is often unsatisfactory, as significant variability can exist - even between different organisms with the same cellular functions. Thus, it has not been possible to adequately understand the source and mechanisms of metal isotopic fractionation. In order to address this problem, we investigated the biological fractionation of Cd isotopes within genetically-modified bacteria (E. coli). There is currently only one known biological use or requirement of Cd, a Cd/Zn carbonic anhydrase (CdCA, from the marine diatom T. weissfloggii), which we introduce into the E. coli genome. We have also developed a cleaning procedure that allows for the treating of bacteria so as to study the isotopic composition of different cellular components. We find that whole cells always exhibit a preference for uptake of the lighter isotopes of Cd. Notably, whole cells appear to have a similar Cd isotopic composition regardless of the expression of CdCA within the E. coli. However, isotopic fractionation can occur within the genetically modified E. coli during Cd use, such that Cd bound in CdCA can display a distinct isotopic composition compared to the cell as a whole. Thus, the externally observed fractionation is independent of the internal uses of Cd, with the largest Cd isotope fractionation occurring during cross-membrane transport. A general implication of these experiments is that trace metal isotopic fractionation most likely reflects metal transport into biological cells (either actively or passively), rather than relating to expression of specific physiological function and genetic expression of different metalloenzymes.

Method for isotopic analysis of chlorinated organic compounds

DOEpatents

Holt, Ben D.; Sturchio, Neil C.

1999-01-01

The present invention provides a method for preparing a VOC sample for carbon and chlorine isotope ratio analysis by mass spectrometer. A VOC sample is placed in a combustion tube and reacted with CuO to form CO.sub.2 and CuCl. The CO.sub.2 is then extracted and analyzed for the carbon isotope ratio. The CuCl is separated from the excess CuO and reacted with CH.sub.3 I to form CH.sub.3 Cl, extracted and analyzed for chlorine isotope ratio.

Stable isotope dilution analysis of hydrologic samples by inductively coupled plasma mass spectrometry

USGS Publications Warehouse

Garbarino, John R.; Taylor, Howard E.

1987-01-01

Inductively coupled plasma mass spectrometry is employed in the determination of Ni, Cu, Sr, Cd, Ba, Ti, and Pb in nonsaline, natural water samples by stable isotope dilution analysis. Hydrologic samples were directly analyzed without any unusual pretreatment. Interference effects related to overlapping isobars, formation of metal oxide and multiply charged ions, and matrix composition were identified and suitable methods of correction evaluated. A comparability study snowed that single-element isotope dilution analysis was only marginally better than sequential multielement isotope dilution analysis. Accuracy and precision of the single-element method were determined on the basis of results obtained for standard reference materials. The instrumental technique was shown to be ideally suited for programs associated with certification of standard reference materials.

Fractionation of Cu and Mo isotopes caused by vapor-liquid partitioning, evidence from the Dahutang W-Cu-Mo ore field

NASA Astrophysics Data System (ADS)

Yao, Junming; Mathur, Ryan; Sun, Weidong; Song, Weile; Chen, Huayong; Mutti, Laurence; Xiang, Xinkui; Luo, Xiaohong

2016-05-01

The study presents δ65Cu and δ97Mo isotope values from cogenetic chalcopyrite and molybdenite found in veins and breccias of the Dahutang W-Cu-Mo ore field in China. The samples span a 3-4 km range. Both isotopes show a significant degree of fractionation. Cu isotope values in the chalcopyrite range from -0.31‰ to +1.48‰, and Mo isotope values in the molybdenite range from -0.03‰ to +1.06‰. For the cogenetic sulfide veined samples, a negative slope relationship exists between δ65Cu and δ97Mo values, which suggest a similar fluid history. Rayleigh distillation models the vein samples' change in isotope values. The breccia samples do not fall on the trend, thus indicating a different source mineralization event. Measured fluid inclusion and δD and δ18O data from cogenetic quartz indicate changes in temperature, and mixing of fluids do not appear to cause the isotopic shifts measure. Related equilibrium processes associated with the partitioning of metal between the vapor-fluid in the hydrothermal system could be the probable cause for the relationship seen between the two isotope systems.

Pollution characteristics and source identification of trace metals in riparian soils of Miyun Reservoir, China.

PubMed

Han, Lanfang; Gao, Bo; Lu, Jin; Zhou, Yang; Xu, Dongyu; Gao, Li; Sun, Ke

2017-10-01

The South-to-North Water Diversion Project, one of China's largest water diversion projects, has aroused widespread concerns about its potential ecological impacts, especially the potential release of trace metals from shoreline soils into Miyun Reservoir (MYR). Here, riparian soil samples from three elevations and four types of land use were collected. Soil particle size distributions, contents and chemical fractionations of trace metals and lead (Pb) isotopic compositions were analyzed. Results showed that soil texture was basically similar in four types of land use, being mainly composed of sand, with minor portions of clay and silt, while recreational land contained more abundant chromium (Cr), copper (Cu), zinc (Zn) and cadmium (Cd), suggesting a possible anthropogenic source for this soil pollution. The potential ecological risk assessment revealed considerable contamination of recreational land, with Cd being the predominant contaminant. Chemical fractionations showed that Cu, arsenic (As), Pb and Cd had potential release risks. Additionally, the 206 Pb/ 207 Pb and 208 Pb/ 207 Pb values of soils were similar to those of coal combustion. By combining principal component analysis (PCA) with Pb isotopic results, coal combustion was identified as the major anthropogenic source of Zn, Cr, Cu, Cd and Pb. Moreover, isotope ratios of Pb fell in the scope of aerosols, indicating that atmospheric deposition may be the primary input pathway of anthropogenic Zn, Cr, Cu, Cd and Pb. Therefore, controlling coal combustion should be a priority to reduce effectively the introduction of additional Zn, Cu, Cd, and Pb to the area in the future. Copyright © 2017 Elsevier Inc. All rights reserved.

Tracing contamination sources in soils with Cu and Zn isotopic ratios.

PubMed

Fekiacova, Z; Cornu, S; Pichat, S

2015-06-01

Copper (Cu) and zinc (Zn) are naturally present and ubiquitous in soils and are important micronutrients. Human activities contribute to the input of these metals to soils in different chemical forms, which can sometimes reach a toxic level for soil organisms and plants. Isotopic signatures could be used to trace sources of anthropogenic Cu and Zn pollution. The aim of this paper is to determine whether it is possible to identify (i) Cu and Zn contamination in soils and their sources, on the basis of their isotopic signatures, and (ii) situations that are a priori favorable or not for tracing Cu and Zn pollution using the isotopic approach. Therefore, we compiled data from the literature on Cu and Zn isotopes in soils, rocks and pollutants and added to this database the results of our own research. As only a few studies have dealt with agricultural contamination, we also studied a soil toposequence from Brittany, France, that experienced spreading of pig slurry for tens of years. In the surface horizons of the natural soils, the δ(65)Cu values vary from -0.15 to 0.44‰ and the δ(66)Zn from -0.03 to 0.43‰. Furthermore, vertical variations along soil profiles range from -0.95 to 0.44‰ for δ(65)Cu and from -0.53 to 0.64‰ for δ(66)Zn values. We concluded that pedogenetic processes can produce isotopic fractionation, yet, it is not always discernible and can be overprinted by an exogenous isotopic signature. Furthermore, some contaminants are enriched in heavy Cu or in light Zn compared to the rock or soil, but no generalization can be made. The anthropogenic inputs can be identified based on stable Cu and Zn isotope ratios if the isotope ratios of the sources are different from those of the soil, which needs to be tested for each individual case. Copyright © 2015 Elsevier B.V. All rights reserved.

Method for isotopic analysis of chlorinated organic compounds

DOEpatents

Holt, B.D.; Sturchio, N.C.

1999-08-24

The present invention provides a method for preparing a VOC sample for carbon and chlorine isotope ratio analysis by mass spectrometer. A VOC sample is placed in a combustion tube and reacted with CuO to form CO{sub 2} and CuCl. The CO{sub 2} is then extracted and analyzed for the carbon isotope ratio. The CuCl is separated from the excess CuO and reacted with CH{sub 3}I to form CH{sub 3}Cl, extracted and analyzed for chlorine isotope ratio. 9 figs.

LA-MC-ICPMS Determination of Copper Isotope Ratios in Turquoise from the Southwestern United States.

NASA Astrophysics Data System (ADS)

Evans, M. J.; Fayek, M.; Riciputi, L.; Anovitz, L.; Hull, S.; Mathien, F. J.; Milford, H.

2004-12-01

Hydrothermal circulation driven by igneous intrusion led to the deposition of turquoise throughout the southwestern United States and Mesoamerica. The genesis of these copper-ore deposits is unclear; conflicting hypotheses call on ascent of magmatic waters (hypogene) or descent and recirculation of meteroric waters (supergene). Copper isotope analyses were performed by laser-ablation multi-collector ICPMS to survey turquoise deposits from AZ, NV, CA, NM, and CO. The turquoise have [Cu] from 0.1 to 10 wt% and are all found in near-surface alteration zones. Analyses of individual turquoise grains are reproducible to better than 0.4\\permil \\delta65Cu (1\\sigma) (relative to NBS-976). \\delta65Cu values show significant variation (ca. 10\\permil) between the deposits, equal to the total range reported for continental ores and both hypogene and supergene deposits. The variability between deposits may reflect differences in source Cu isotopic composition or more likely, hydrothermal processes during leaching and deposition. The mining and trade of turquoise played an important role in early social and economic development between Mesoamerica and N. America. Copper isotopes will improve differentiation between turquoise source areas, aiding archaeological and cultural studies of trade between and within Mesoamerica and the SW USA. Research sponsored by NSF-BCS (Archaeology) grant #0312088 to Fayek and the Office of Basic Energy Sciences, U.S. Department of Energy, under contract with Oak Ridge National Laboratory, managed by UT-Battelle, LLC. The submitted manuscript has been authored by a contractor of the U.S. Government under contract No. DE-AC05-00OR22725. Accordingly, the U.S. Government retains a nonexclusive, royalty-free license to publish or reproduce the published form of this contribution, or allow others to do so, for U.S. Government purposes.

Determining the N and O isotope effects of microbial nitrite reduction: the global N cycle implications of an enzyme-dependent isotope effect

NASA Astrophysics Data System (ADS)

Martin, T. S.; Casciotti, K. L.

2014-12-01

The marine nitrogen (N) cycle is a dynamic system of critical importance, since nitrogen is the limiting nutrient in over half of the world's oceans. Denitrification and anammox, the main N loss processes from the ocean, have different effects on carbon cycling and greenhouse gas emission. Understanding the balance between the two processes is vital to understanding the role of the N cycle in global climate change. One approach for investigating these processes is by using stable isotope analysis to estimate the relative magnitudes of N fluxes, particularly for biologically mediated processes. In order to make the most of the currently available isotope analysis techniques, it is necessary to know the isotope effects for each processes occurring in the environment. Nitrite reduction is an important step in denitrification. Previous work had begun to explore the N isotope effects for nitrite reduction, but no oxygen (O) isotope effect has been measured. Additionally, no consideration has been given to the type of nitrite reductase carrying out the reaction. There are two main types of respiratory nitrite reductase, one that is Cu-based and another that is Fe-based. We performed batch culture experiments with denitrifier strains possessing either a Cu-type or Fe-type nitrite reductase. Both N and O isotope effects for nitrite reduction were determined for each of these experiments by measuring the NO2- concentration, as well as the N and O isotopes of nitrite and applying a Rayleigh fractionation model. Both the N and O isotope effects were found to be significantly different between the two types of enzymes. This enzyme-linked difference in isotope effects emphasizes the importance of microbial community composition within the global N cycle.

Stable Cu and Zn isotope ratios as tracers of sources and transport of Cu and Zn in contaminated soil

NASA Astrophysics Data System (ADS)

Bigalke, Moritz; Weyer, Stefan; Kobza, Jozef; Wilcke, Wolfgang

2010-12-01

Copper and Zn metals are produced in large quantities for different applications. During Cu production, large amounts of Cu and Zn can be released to the environment. Therefore, the surroundings of Cu smelters are frequently metal-polluted. We determined Cu and Zn concentrations and Cu and Zn stable isotope ratios (δ 65Cu, δ 66Zn) in three soils at distances of 1.1, 3.8, and 5.3 km from a Slovak Cu smelter and in smelter wastes (slag, sludge, ash) to trace sources and transport of Cu and Zn in soils. Stable isotope ratios were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in total digests. Soils were heavily contaminated with concentrations up to 8087 μg g -1 Cu and 2084 μg g -1 Zn in the organic horizons. The δ 65Cu values varied little (-0.12‰ to 0.36‰) in soils and most wastes and therefore no source identification was possible. In soils, Cu became isotopically lighter with increasing depth down to 0.4 m, likely because of equilibrium reactions between dissolved and adsorbed Cu species during transport of smelter-derived Cu through the soil. The δ 66Zn IRMM values were isotopically lighter in ash (-0.41‰) and organic horizons (-0.85‰ to -0.47‰) than in bedrock (-0.28‰) and slag (0.18‰) likely mainly because of kinetic fractionation during evaporation and thus allowed for separation of smelter-Zn from native Zn in soil. In particular in the organic horizons large variations in δ 66Zn values occur, probably caused by biogeochemical fractionation in the soil-plant system. In the mineral horizons, Zn isotopes showed only minor shifts to heavier δ 66Zn values with depth mainly because of the mixing of smelter-derived Zn and native Zn in the soils. In contrast to Cu, Zn isotope fractionation between dissolved and adsorbed species was probably only a minor driver in producing the observed variations in δ 66Zn values. Our results demonstrate that metal stable isotope ratios may serve as tracer of sources, vertical dislocation, and biogeochemical behavior in contaminated soil.

Coper Isotope Fractionation in Porphyry Copper Deposits: A Controlled Experiment

NASA Astrophysics Data System (ADS)

Ruiz, J.; Mathur, R.; Uhrie, J. L.; Hiskey, B.

2001-12-01

Previous studies have shown that copper is fractionated in the environment. However, the mechanisms for isotope fractionation and the role of organic and inorganic processes in the fractionation are not well understood. Here we used the well controlled experiments used by Phelps Dodge Corporation aimed at leaching copper from their ore deposits to constrain the mechanism of copper isotope fractionation in natural systems. The isotope data were collected on a Micromass Isoprobe. High temperature copper sulfides from ore deposits in Chile and Arizona yield delta 65Cu near 0 permil. The reproducibility of the data is better that 0.1 permil. Controlled experiments consisting of large columns of rocks were fed solutions containing bacteria such as Thiobacillus ferroxidans and Leptospirrilium ferroxidan. Solutions fom the columns were sampled for sixty days and analyzed for copper concentrations, oxidation potential, ferrous/ferric ratios and pH. The results indicate that the bacterially aided dissolution of copper fractionated copper. Preliminary experiments of copper dissolution not using bacteria show no isotope fractionation The original rock in the experiment has a delta 65Cu of -2.1. The first solutions that were collected from the columns had a delta 65Cu of -5.0 per mil. The liquid changed its isotopic composition from -50 to -10 during the sixty days of sampling. The greatest shift in the isotope ratios occurred the first 30 days when the copper recovered was less than 40% and the ferrous/ferric ratios were somewhat constant. At approximately 35 days after the start of the experiments, the copper recovery increases the ferrousferric ratio decreased and the copper isotope ratio of the fluids remained fairly constant. The data suggest that the bacteria are required to effectively fractionate copper isotopes in natural systems and that the mechanisms of bacterial aided copper dissolution may include a direct dissolution of the sulfides by the bacteria. Experiments underway with enzimes without the bacteria may confirm this hypothesis. The data obtained in these experiments will provide some constraints in the use of copper isotopes as proxy for life in the rock record.

Lead isotopes in lichen transplants around a Cu smelter in Russia determined by MC-ICP-MS reveal transient records of multiple sources.

PubMed

Spiro, B; Weiss, D J; Purvis, O W; Mikhailova, I; Williamson, B J; Coles, B J; Udachin, V

2004-12-15

Transplants of the lichen Hypogymnia physodes, which is relatively tolerant to SO2 and heavy metals, were deployed for 3 months over a 60 km long SW-NE transect centered on a highly polluting Cu smelter and its adjoining town of Karabash, southern Urals, Russia. The abundance of 206Pb, 207Pb, 208Pb, and 204Pb were determined by MC-ICP-MS. The measurement of 204Pb revealed critical features, which would otherwise remain concealed: (i) The precise isotope ratios referenced to 204Pb allowed several different sources to be resolved even within the small area covered: (a) the obvious pollutant source of the Karabash Cu smelter; (b) two dispersed sources, likely to include soil with lower and different contributions of thorogenic and uranogenic lead; and (c) one anthropogenic source with higher contribution of 235U derived Pb. (ii) In part of the transect, the Pb isotope composition changed while the Pb concentrations remained the same. This indicates that the Pb content of the transplantation material from the background site was largely replaced and that the transplants provide a transient record reflecting a continuous accumulation and loss of environmental Pb, probably mainly in the form of extracellular particles. Overall, the method of lichen transplantation coupled with Pb isotope ratio determinations proved effective in assessing the usefulness of lichens in biomonitoring and in resolving different sources of atmospheric deposition.

Tennantite-tetrahedrite series from the Madan Pb-Zn deposits, Central Rhodopes, Bulgaria

NASA Astrophysics Data System (ADS)

Vassileva, Rossitsa D.; Atanassova, Radostina; Kouzmanov, Kalin

2014-08-01

Minerals from the tennantite-tetrahedrite series (fahlores) are found as single euhedral crystals and crustiform aggregates in hydrothermal veins of the Gradishte and Petrovitsa Pb-Zn deposits of the Madan ore field, southern Bulgaria. Unusually large compositional variations and fine oscillatory crystal zoning were investigated with electron microprobe analysis. The Gradishte samples correspond dominantly to tennantite, while Petrovitsa crystals have exclusively tetrahedrite composition. Fahlore compositions at Madan correspond to zincian varieties (1.6-1.95 apfu), with low Fe-content (<0.45 apfu). Minor silver is characteristic only for the Petrovitsa samples, reaching a maximum of 0.30 apfu. The (Cu+Ag) content of the Petrovitsa tennantites and the Cu content of the Gradishte tetrahedrites systematically exceed 10 apfu resulting in compensation of the excess Cu in the structure by Fe3+. Textural characteristics, mineral relationships and available fluid inclusion and stable isotope data suggest that fahlores precipitated in the late stages of mineralization at Madan, at temperature interval of 300-200 °C from oxidizing fluids with mixed (magmatic-meteoric) signatures.

Modifying current-voltage characteristics of a single molecule junction by isotope substitution: OHOD dimer on Cu(110)

NASA Astrophysics Data System (ADS)

Okuyama, H.; Shiotari, A.; Kumagai, T.; Hatta, S.; Aruga, T.; Ootsuka, Y.; Paulsson, M.; Ueba, H.

2012-05-01

Vibrationally induced configurational change and nonlinear current-voltage (I-V) characteristics are investigated within the scanning tunneling microscope (STM) junction, including hydroxyl dimers on a Cu(110) surface. H-bonded hydroxyl dimers composed of OH and/or OD have a unique inclined geometry that can be switched back and forth by vibrational excitations via the inelastic electron tunneling process of the STM. The relative occupation change between the high- and low-conductance states as a function of bias voltage critically depends on the isotopic compositions, and thus the I-V characteristics can be modified to exhibit negative differential resistance by H/D substitution. The experimental results of the occupation change and I-V curves are nicely reproduced using a recently proposed analytical model combined with comprehensive density functional calculations for the input parameters (vibrational modes and their emission rates by tunneling electrons, conductance, and relative occupation change of high- and low-conductance states), and they underlines the different roles played by the free and shared O-H(D) stretch modes of the hydroxyl dimers on a Cu(110) surface.

Separation of copper, iron, and zinc from complex aqueous solutions for isotopic measurement

USGS Publications Warehouse

Borrok, D.M.; Wanty, R.B.; Ridley, W.I.; Wolf, R.; Lamothe, P.J.; Adams, M.

2007-01-01

The measurement of Cu, Fe, and Zn isotopes in natural samples may provide valuable information about biogeochemical processes in the environment. However, the widespread application of stable Cu, Fe, and Zn isotope chemistry to natural water systems remains limited by our ability to efficiently separate these trace elements from the greater concentrations of matrix elements. In this study, we present a new method for the isolation of Cu, Fe, and Zn from complex aqueous solutions using a single anion-exchange column with hydrochloric acid media. Using this method we are able to quantitatively separate Cu, Fe, and Zn from each other and from matrix elements in a single column elution. Elution of the elements of interest, as well as all other elements, through the anion-exchange column is a function of the speciation of each element in the various concentrations of HCl. We highlight the column chemistry by comparing our observations with published studies that have investigated the speciation of Cu, Fe, and Zn in chloride solutions. The functionality of the column procedure was tested by measuring Cu, Fe, and Zn isotopes in a variety of stream water samples impacted by acid mine drainage. The accuracy and precision of Zn isotopic measurements was tested by doping Zn-free stream water with the Zn isotopic standard. The reproducibility of the entire column separation process and the overall precision of the isotopic measurements were also evaluated. The isotopic results demonstrate that the Cu, Fe, and Zn column separates from the tested stream waters are of sufficient purity to be analyzed directly using a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS), and that the measurements are fully-reproducible, accurate, and precise. Although limited in scope, these isotopic measurements reveal significant variations in ??65Cu (- 1.41 to + 0.30???), ??56Fe (- 0.56 to + 0.34???), and ??66Zn (0.31 to 0.49???) among samples collected from different abandoned mines within a single watershed. Hence, Cu, Fe, and Zn isotopic measurements may be a powerful tool for fingerprinting specific metal sources and/or examining biogeochemical reactions within fresh water systems.

Iron isotope behavior during fluid/rock interaction in K-feldspar alteration zone - A model for pyrite in gold deposits from the Jiaodong Peninsula, East China

NASA Astrophysics Data System (ADS)

Zhu, Zhi-Yong; Jiang, Shao-Yong; Mathur, Ryan; Cook, Nigel J.; Yang, Tao; Wang, Meng; Ma, Liang; Ciobanu, Cristiana L.

2018-02-01

Mechanisms for Fe isotope fractionation in hydrothermal mineral deposits and in zones of associated K-feldspar alteration remain poorly constrained. We have analyzed a suite of bulk samples consisting of granite displaying K-feldspar alteration, Precambrian metamorphic rocks, and pyrite from gold deposits of the Jiaodong Peninsula, East China, by multi-collector inductively-coupled plasma mass spectrometry. Pyrites from disseminated (J-type) ores show a δ56Fe variation from +0.01 to +0.64‰, overlapping with the signature of the host granites (+0.08 to +0.39‰). In contrast, pyrites from quartz veins (L-type ores) show a wide range of Fe-isotopic composition from -0.78 to +0.79‰. Negative values are never seen in the J-type pyrites. The Fe isotope signature of the host granite with K-feldspar alteration is significantly heavier than that of the bulk silicate Earth. The Fe isotopic compositions of Precambrian metamorphic rocks across the district display a narrow range between -0.16‰ and +0.19‰, which is similar to most terrestrial rocks. Concentrations of major and trace elements in bulk samples were also determined, so as to evaluate any correlation between Fe isotope composition and degree of alteration. We note that during progressive K-feldspar alteration to rocks containing >70 wt% SiO2, >75 ppm Rb, and <1.2 wt% total Fe2O3, the Fe isotope composition of the granite changes systematically. The Fe isotope signature becomes heavier as the degree of alteration increases. The extremely light Fe isotopic compositions in L-type gold deposits may be explained by Rayleigh fractionation during pyrite precipitation in an open fracture system. We note that the sulfur isotopic compositions of pyrite in the two types of ores are also different. Pyrite from J-type ores has a systematically 3.5‰-higher δ34S value (11.2‰) than those of pyrite from the L-type ores (7.7‰). There is, however, no correlation between Fe and S isotope signatures. The isotopic fractionation of sulfur is used to constrain a change in the fO2 of the hydrothermal fluids from which pyrite precipitated. This work demonstrates that the Fe isotope composition of pyrite displays a significant response to the process of pyrite precipitation in hydrothermal systems, and that systematic fractionation of iron isotopes occurs during fluid/rock reaction in the K-feldspar alteration zone of the Linglong granite. The implications of the results are that processes of mineralization and associated fluid-rock interaction, which are ubiquitously observed in porphyry-style Cu-Au-Mo and other hydrothermal deposits, may be readily traceable using Fe isotopes.

Copper in soil fractions and runoff in a vineyard catchment: Insights from copper stable isotopes.

PubMed

Babcsányi, Izabella; Chabaux, François; Granet, Mathieu; Meite, Fatima; Payraudeau, Sylvain; Duplay, Joëlle; Imfeld, Gwenaël

2016-07-01

Understanding the fate of copper (Cu) fungicides in vineyard soils and catchments is a prerequisite to limit the off-site impact of Cu. Using Cu stable isotopes, Cu retention in soils and runoff transport was investigated in relation to the use of Cu fungicides and the hydrological conditions in a vineyard catchment (Rouffach, Haut-Rhin, France; mean slope: 15%). The δ(65)Cu values of the bulk vineyard soil varied moderately through the depth of the soil profiles (-0.12 to 0.24‰±0.08‰). The values were in the range of those of the fungicides (-0.21 to 0.11‰) and included the geogenic δ(65)Cu value of the untreated soil (0.08‰). However, δ(65)Cu values significantly differed between particle-size soil fractions (-0.37±0.10‰ in fine clays and 0.23±0.07‰ in silt). Together with the soil mineralogy, the results suggested Cu isotope fractionation primarily associated with the clay and fine clay fractions that include both SOM and mineral phases. The vegetation did not affect the Cu isotope patterns in the vineyard soils. Cu export by runoff from the catchment accounted for 1% of the applied Cu mass from 11th May to 20(th) July 2011, covering most of the Cu use period. 84% of the exported Cu mass was Cu bound to suspended particulate matter (SPM). The runoff displayed δ(65)Cu values from 0.52 to 1.35‰ in the dissolved phase (<0.45μm) compared to -0.34 to -0.02‰ in the SPM phase, indicating that clay and fine clay fractions were the main vectors of SPM-bound Cu in runoff. Overall, this study shows that Cu stable isotopes may allow identifying the Cu distribution in the soil fractions and their contribution to Cu export in runoff from Cu-contaminated catchments. Copyright © 2016 Elsevier B.V. All rights reserved.

Copper isotope fractionation during surface adsorption and intracellular incorporation by bacteria

PubMed Central

Navarrete, Jesica U.; Borrok, David M.; Viveros, Marian; Ellzey, Joanne T.

2011-01-01

Copper isotopes may prove to be a useful tool for investigating bacteria–metal interactions recorded in natural waters, soils, and rocks. However, experimental data which attempt to constrain Cu isotope fractionation in biologic systems are limited and unclear. In this study, we utilized Cu isotopes (δ65Cu) to investigate Cu–bacteria interactions, including surface adsorption and intracellular incorporation. Experiments were conducted with individual representative species of Gram-positive (Bacillus subtilis) and Gram-negative (Escherichia coli) bacteria, as well as with wild-type consortia of microorganisms from several natural environments. Ph-dependent adsorption experiments were conducted with live and dead cells over the pH range 2.5–6. Surface adsorption experiments of Cu onto live bacterial cells resulted in apparent separation factors (Δ65Cusolution–solid = δ65Cusolution – δ65Cusolid) ranging from +0.3‰ to +1.4‰ for B. subtilis and +0.2‰ to +2.6‰ for E. coli. However, because heat-killed bacterial cells did not exhibit this behavior, the preference of the lighter Cu isotope by the cells is probably not related to reversible surface adsorption, but instead is a metabolically-driven phenomenon. Adsorption experiments with heat-killed cells yielded apparent separation factors ranging from +0.3‰ to –0.69‰ which likely reflects fractionation from complexation with organic acid surface functional group sites. For intracellular incorporation experiments the lab strains and natural consortia preferentially incorporated the lighter Cu isotope with an apparent Δ65Cusolution–solid ranging from ~+1.0‰ to +4.4‰. Our results indicate that live bacterial cells preferentially sequester the lighter Cu isotope regardless of the experimental conditions. The fractionation mechanisms involved are likely related to active cellular transport and regulation, including the reduction of Cu(II) to Cu(I). Because similar intracellular Cu machinery is shared by fungi, plants, and higher organisms, the influence of biological processes on the δ65Cu of natural waters and soils is probably considerable. PMID:21785492

Tracing sources of crustal contamination using multiple S and Fe isotopes in the Hart komatiite-associated Ni-Cu-PGE sulfide deposit, Abitibi greenstone belt, Ontario, Canada

NASA Astrophysics Data System (ADS)

Hiebert, R. S.; Bekker, A.; Houlé, M. G.; Wing, B. A.; Rouxel, O. J.

2016-10-01

Assimilation by mafic to ultramafic magmas of sulfur-bearing country rocks is considered an important contributing factor to reach sulfide saturation and form magmatic Ni-Cu-platinum group element (PGE) sulfide deposits. Sulfur-bearing sedimentary rocks in the Archean are generally characterized by mass-independent fractionation of sulfur isotopes that is a result of atmospheric photochemical reactions, which produces isotopically distinct pools of sulfur. Likewise, low-temperature processing of iron, through biological and abiotic redox cycling, produces a range of Fe isotope values in Archean sedimentary rocks that is distinct from the range of the mantle and magmatic Fe isotope values. Both of these signals can be used to identify potential country rock assimilants and their contribution to magmatic sulfide deposits. We use multiple S and Fe isotopes to characterize the composition of the potential iron and sulfur sources for the sulfide liquids that formed the Hart deposit in the Shaw Dome area within the Abitibi greenstone belt in Ontario (Canada). The Hart deposit is composed of two zones with komatiite-associated Ni-Cu-PGE mineralization; the main zone consists of a massive sulfide deposit at the base of the basal flow in the komatiite sequence, whereas the eastern extension consists of a semi-massive sulfide zone located 12 to 25 m above the base of the second flow in the komatiite sequence. Low δ56Fe values and non-zero δ34S and Δ33S values of the komatiitic rocks and associated mineralization at the Hart deposit is best explained by mixing and isotope exchange with crustal materials, such as exhalite and graphitic argillite, rather than intrinsic fractionation within the komatiite. This approach allows tracing the extent of crustal contamination away from the deposit and the degree of mixing between the sulfide and komatiite melts. The exhalite and graphitic argillite were the dominant contaminants for the main zone of mineralization and the eastern extension zone of the Hart deposit, respectively. Critically, the extent of contamination, as revealed by multiple S and Fe isotope systematics, is greatest within the deposit and decreases away from it within the komatiite flow. This pattern points to a local source of crustal contamination for the mantle-derived komatiitic melt and a low degree of homogenization between the mineralization and the surrounding lava flow. Coupled S and Fe isotope patterns like those identified at the Hart deposit may provide a useful tool for assessing the potential of a komatiitic sequence to host Ni-Cu-(PGE).

Comparison of Dilution, Filtration, and Microwave Digestion Sample Pretreatments in Elemental Profiling of Wine by ICP-MS.

PubMed

Godshaw, Joshua; Hopfer, Helene; Nelson, Jenny; Ebeler, Susan E

2017-09-25

Wine elemental composition varies by cultivar, geographic origin, viticultural and enological practices, and is often used for authenticity validation. Elemental analysis of wine by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is challenging due to the potential for non-spectral interferences and plasma instability arising from organic matrix components. Sample preparation mitigates these interferences, however, conflicting recommendations of best practices in ICP-MS analysis of wine have been reported. This study compared direct dilution, microwave-assisted acid digestion, and two filtration sample pretreatments, acidification prior to filtration and filtration followed by acidification, in elemental profiling of one white and three red table wines by ICP-MS. Of 43 monitored isotopes, 37 varied by sample preparation method, with significantly higher results of 17 isotopes in the microwave-digested samples. Both filtration treatments resulted in lower results for 11 isotopes compared to the other methods. Finally, isotope dilution determination of copper based on natural abundances and the 63 Cu: 65 Cu instrument response ratio agreed with external calibration and confirmed a significant sample preparation effect. Overall, microwave digestion did not compare favorably, and direct dilution was found to provide the best compromise between ease of use and result accuracy and precision, although all preparation strategies were able to differentiate the wines.

Novel and non-traditional use of stable isotope tracers to study metal bioavailability from natural particles

USGS Publications Warehouse

Croteau, Marie-Noële; Cain, Daniel J.; Fuller, Christopher C.

2013-01-01

We devised a novel tracing approach that involves enriching test organisms with a stable metal isotope of low natural abundance prior to characterizing metal bioavailability from natural inorganic particles. In addition to circumventing uncertainties associated with labeling natural particles and distinguishing background metals, the proposed "reverse labeling" technique overcomes many drawbacks inherent to using radioisotope tracers. Specifically, we chronically exposed freshwater snails (Lymnaea stagnalis) to synthetic water spiked with Cu that was 99.4% 65Cu to increase the relative abundance of 65Cu in the snail’s tissues from 32% to >80%. The isotopically enriched snails were then exposed to benthic algae mixed with Cu-bearing Fe–Al particles collected from the Animas River (Colorado), an acid mine drainage impacted river. We used 63Cu to trace Cu uptake from the natural particles and inferred their bioavailability from calculation of Cu assimilation into tissues. Cu assimilation from these particles was 44%, indicating that 44% of the particulate Cu was absorbed by the invertebrate. This demonstrates that inorganic particulate Cu can be bioavailable. The reverse labeling approach shows great potential in various scientific areas such as environmental contamination and nutrition for addressing questions involving uptake of an element that naturally has multiple isotopes.

Re-Os isotopic evidence for an enriched-mantle source for the Noril'sk-type, ore-bearing intrusions, Siberia

USGS Publications Warehouse

Walker, R.J.; Morgan, J.W.; Horan, M.F.; Czamanske, G.K.; Krogstad, E.J.; Fedorenko, V.A.; Kunilov, V.E.

1994-01-01

Magmatic Cu-Ni sulfide ores and spatially associated ultramafic and mafic rocks from the Noril'sk I, Talnakh, and Kharaelakh intrusions are examined for Re-Os isotopic systematics. Neodymium and lead isotopic data also are reported for the ultramafic and mafic rocks. The Re-Os data for most samples indicate closed-system behavior since the ca. 250 Ma igneous crystallization age of the intrusions. There are small but significant differences in the initial osmium isotopic compositions of samples from the three intrusions. Ores from the Noril'sk I intrusion have ??Os values that vary from +0.4 to +8.8, but average +5.8. Ores from the Talnakh intrusion have ??Os values that range from +6.7 to +8.2, averaging +7.7. Ores from the Kharaelakh intrusion have ??Os values that range from +7.8 to +12.9, with an average value of +10.4. The osmium isotopic compositions of the ore samples from the Main Kharaelakh orebody exhibit minimal overlap with those for the Noril'sk I and Talnakh intrusions, indicating that these Kharaelakh ores were derived from a more radiogenic source of osmium than the other ores. Combined osmium and lead data for major orebodies in the three intrusions plot in three distinct fields, indicating derivation of osmium and lead from at least three isotopically distinct sources. Some of the variation in lead isotopic compositions may be the result of minor lower-crustal contamination. However, in contrast to most other isotopic and trace element data, Os-Pb variations are generally inconsistent with significant crustal contamination or interaction with the subcontinental lithosphere. Thus, the osmium and lead isotopic compositions of these intrusions probably reflect quite closely the compositions of their mantle source, and suggest that these two isotope systems were insensitive to lithospheric interaction. Ultramafic and mafic rocks have osmium and lead isotopic compositions that range only slightly beyond the compositions of the ores. These rocks also have relatively uniform ??{lunate}Nd values that range only from -0.8 to + 1.1. This limited variation in neodymium isotopic composition may reflect the characteristics of the mantle sources of the rocks, or it may indicate that somehow similar proportions of crust contaminated the parental melts. The osmium, lead, and neodymium isotopic data for these rocks most closely resemble the mantle sources of certain ocean island basalts (OIB), such as some Hawaiian basalts. Hence, these data are consistent with derivation of primary melts from a mantle source similar to that of some types of hotspot activity. The long-term Re/Os enrichment of this and similar mantle sources, relative to chondritic upper mantle, may reflect 1. (1) incorporation of recycled oceanic crust into the source more than 1 Ga ago, 2. (2) derivation from a mantle plume that originated at the outer core-lower mantle interface, or 3. (3) persistence of primordial stratification of rhenium and osmium in the mantle. ?? 1994.

Lead isotopic fingerprinting of aerosols to characterize the sources of atmospheric lead in an industrial city of India

NASA Astrophysics Data System (ADS)

Sen, Indra S.; Bizimis, Michael; Tripathi, Sachchida Nand; Paul, Debajyoti

2016-03-01

Anthropogenic Pb in the environment is primarily sourced from combustion of fossil fuel and high-temperature industries such as smelters. Identifying the sources and pathways of anthropogenic Pb in the environment is important because Pb toxicity is known to have adverse effects on human health. Pb pollution sources for America, Europe, and China are well documented. However, sources of atmospheric Pb are unknown in India, particularly after leaded gasoline was phased out in 2000. India has a developing economy with a rapidly emerging automobile and high temperature industry, and anthropogenic Pb emission is expected to rise in the next decade. In this study, we report on the Pb-isotope compositions and trace metal ratios of airborne particulates collected in Kanpur, a large city in northern part of India. The study shows that the PM10 aerosols had elevated concentration of Cd, Pb, Zn, As, and Cu in the Kanpur area, however their concentrations are well below the United States Environmental Protection Agency chronic exposure limit. Lead isotopic and trace metal data reveal industrial emission as the plausible source of anthropogenic Pb in the atmosphere in Kanpur. However, Pb isotopic compositions of potential source end-members are required to fully evaluate Pb contamination in India over time. This is the first study that characterizes the isotopic composition of atmospheric Pb in an Indian city after leaded gasoline was phased out by 2000.

Petrogenesis of the late Early Cretaceous granodiorite - Quartz diorite from eastern Guangdong, SE China: Implications for tectono-magmatic evolution and porphyry Cu-Au-Mo mineralization

NASA Astrophysics Data System (ADS)

Jia, Lihui; Mao, Jingwen; Liu, Peng; Li, Yang

2018-04-01

Comprehensive petrological, zircon U-Pb dating, Hf-O isotopes, whole rock geochemistry and Sr-Nd isotopes data are presented for the Xinwei and Sanrao intrusions in the eastern Guangdong Province, Southeast (SE) China, with an aim to constrain the petrogenesis, tectono-magmatic evolution and evaluate the implication for porphyry Cu-Au-Mo mineralization. The Xinwei intrusion is composed of granodiorite and quartz diorite, whilst the Sanrao intrusion consists of granodiorite. Zircon U-Pb ages show that both intrusions were emplaced at ca. 106-102 Ma. All rocks are metaluminous to weakly peraluminous, high-K calc-alkaline in composition, and they are characterized by LREEs enrichment, depletion in Nb, Ta, P, and Ti, and strongly fractionated LREEs to HREEs. The initial 87Sr/86Sr ratios range from 0.7055 to 0.7059, and εNd(t) values range from -3.9 to -3.0. Together with the relatively high εHf(t) values (-3.2 to 3.3) and low δ18O values (4.9‰ to 6.6‰), these data suggest that the Xinwei and Sanrao intrusions were derived from a mixed source: including the mantle-derived mafic magmas and lower continental crustal magmas. Fractional crystallization played an important role in the magmatic evolution of the Xinwei and Sanrao intrusions. The elemental and isotopic compositions of the Xinwei and Sanrao intrusions, as well as the high water content and oxidation state of their parental magmas, are similar to those of the ore-bearing granodiorites of the Luoboling porphyry Cu-Mo deposit in the Fujian Province, neighbouring east to the Guangdong Province, indicating that the late Early Cretaceous granodioritic intrusions in the eastern Guangdong Province may also have Cu-Au-Mo mineralization potential. The late Early Cretaceous magmatic event is firstly reported in eastern Guangdong, and represents a positive response of large-scale lithosphere extension and thinning, triggered by the changing subduction direction of the Paleo-Pacific plate from oblique subduction to parallel to the continental margin during the Early Cretaceous.

The role of bacterial consortium and organic amendment in Cu and Fe isotope fractionation in plants on a polluted mine site.

PubMed

Pérez Rodríguez, Nathalie; Langella, Francesca; Rodushkin, Ilia; Engström, Emma; Kothe, Erika; Alakangas, Lena; Öhlander, Björn

2014-01-01

Copper and iron isotope fractionation by plant uptake and translocation is a matter of current research. As a way to apply the use of Cu and Fe stable isotopes in the phytoremediation of contaminated sites, the effects of organic amendment and microbial addition in a mine-spoiled soil seeded with Helianthus annuus in pot experiments and field trials were studied. Results show that the addition of a microbial consortium of ten bacterial strains has an influence on Cu and Fe isotope fractionation by the uptake and translocation in pot experiments, with an increase in average of 0.99 ‰ for the δ(65)Cu values from soil to roots. In the field trial, the amendment with the addition of bacteria and mycorrhiza as single and double inoculation enriches the leaves in (65)Cu compared to the soil. As a result of the same trial, the δ(56)Fe values in the leaves are lower than those from the bulk soil, although some differences are seen according to the amendment used. Siderophores, possibly released by the bacterial consortium, can be responsible for this change in the Cu and Fe fractionation. The overall isotopic fractionation trend for Cu and Fe does not vary for pot and field experiments with or without bacteria. However, variations in specific metabolic pathways related to metal-organic complexation and weathering can modify particular isotopic signatures.

Using trace element content and lead isotopic composition to assess sources of PM in Tijuana, Mexico

NASA Astrophysics Data System (ADS)

Salcedo, D.; Castro, T.; Bernal, J. P.; Almanza-Veloz, V.; Zavala, M.; González-Castillo, E.; Saavedra, M. I.; Perez-Arvízu, O.; Díaz-Trujillo, G. C.; Molina, L. T.

2016-05-01

PM2.5 samples were collected at two urban sites (Parque Morelos (PQM) and CECyTE (CEC)) in Tijuana during the Cal-Mex campaign from May 24 to June 5, 2010. Concentration of trace elements (Mg, Al, Ti, V, Mn, Fe, Co, Ni, Zn, Cu, Ga, As, Se, Rb, Sr, Mo, Cd, Sn, Sb, Ba, La, Ce, and Pb), and Pb isotopic composition were determined in order to study the sources of PM impacting each site. Other chemical analysis (gravimetric, elemental and organic carbon (EC/OC), and polycyclic aromatic hydrocarbons (PAHs)), were also performed. Finally, back-trajectories were calculated to facilitate the interpretation of the chemical data. Trace elements results show that CEC is a receptor site affected by mixed regional sources: sea salt, mineral, urban, and industrial. On the other hand, PQM seems to be impacted mainly by local sources. In particular, Pb at CEC is of anthropogenic, as well as crustal origin. This conclusion is supported by the lead isotopic composition, whose values are consistent with a combination of lead extracted from US mines, and lead from bedrocks in the Mexican Sierras. Some of the time variability observed can be explained using the back-trajectories.

Isotopically modified nanoparticles for enhanced detection in bioaccumulation studies

USGS Publications Warehouse

Misra, S.K.; Dybowska, A.; Berhanu, D.; Croteau, M.-N.; Luoma, S.N.; Boccaccini, A.R.; Valsami-Jones, E.

2012-01-01

This work presents results on synthesis of isotopically enriched (99% 65Cu) copper oxide nanoparticles and its application in ecotoxicological studies. 65CuO nanoparticles were synthesized as spheres (7 nm) and rods (7 ?? 40 nm). Significant differences were observed between the reactivity and dissolution of spherical and rod shaped nanoparticles. The extreme sensitivity of the stable isotope tracing technique developed in this study allowed determining Cu uptake at exposure concentrations equivalent to background Cu concentrations in freshwater systems (0.2-30 ??g/L). Without a tracer, detection of newly accumulated Cu was impossible, even at exposure concentrations surpassing some of the most contaminated water systems (>1 mg/L). ?? 2011 American Chemical Society.

First total-absorption spectroscopy measurement on the neutron-rich Cu isotopes

NASA Astrophysics Data System (ADS)

Naqvi, F.; Spyrou, A.; Liddick, S. N.; Larsen, A. C.; Guttormsen, M.; Bleuel, D. L.; Campo, L. C.; Couture, A.; Crider, B. P.; Dombos, A. C.; Ginter, T.; Lewis, R.; Mosby, S.; Perdikakis, G.; Prokop, C. P.; Quinn, S. J.; Renstrom, T.; Rubio, B.; Siem, S.

2015-10-01

The first beta-decay studies of 73-71Cu isotopes using the Total Absorption Spectroscopy (TAS) will be reported. The Cu isotopes have one proton outside the Z = 28 shell and hence are good candidates to probe the single-particle structure in the region.Theories predict weakening of the Z = 28 shell gap due to the tensor interaction between the valence πν single-particle orbitals. Comparing the beta-decay strength distributions in the daughter Zn isotopes to the theoretical calculations will provide a stringent test of the predictions. The experiment was performed at the National Superconducting Cyclotron Laboratory (NSCL) employing the TAS technique with the Summing NaI(Tl) detector, while beta decays were measured in the NSCL beta-counting system. The experimentally obtained total absorption spectra for the neutron-rich Cu isotopes will be presented and the implications of the extracted beta-feeding intensities will be discussed.

Hypoxia induces copper stable isotope fractionation in hepatocellular carcinoma, in a HIF-independent manner.

PubMed

Bondanese, Victor P; Lamboux, Aline; Simon, Melanie; Lafont, Jérôme E; Albalat, Emmanuelle; Pichat, Sylvain; Vanacker, Jean-Marc; Telouk, Philippe; Balter, Vincent; Oger, Philippe; Albarède, Francis

2016-11-09

Hepatocellular carcinoma (HCC) is the most frequent type of primary liver cancer, with increasing incidence worldwide. The unrestrained proliferation of tumour cells leads to tumour hypoxia which in turn promotes cancer aggressiveness. While changes in the concentration of copper (Cu) have long been observed upon cancerization, we have recently reported that the isotopic composition of copper is also altered in several types of cancer. In particular, we showed that in hepatocellular carcinoma, tumour tissue contains heavier copper compared to the surrounding parenchyma. However, the reasons behind such isotopic signature remained elusive. Here we show that hypoxia causes heavy copper enrichment in several human cell lines. We also demonstrate that this effect of hypoxia is pH, HIF-1 and -2 independent. Our data identify a previously unrecognized cellular process associated with hypoxia, and suggests that in vivo tumour hypoxia determines copper isotope fractionation in HCC and other solid cancers.

Occurrence of selected trace metals and their oral bioaccessibility in urban soils of kindergartens and parks in Bratislava (Slovak Republic) as evaluated by simple in vitro digestion procedure.

PubMed

Hiller, Edgar; Mihaljevič, Martin; Filová, Lenka; Lachká, Lucia; Jurkovič, Ľubomír; Kulikova, Tatsiana; Fajčíková, Katarína; Šimurková, Mária; Tatarková, Veronika

2017-10-01

A total of eighty surface soil samples were collected from public kindergartens and urban parks in the city of Bratislava, and the <150µm soil fraction was evaluated for total concentrations of five metals, Cd, Cu, Hg, Pb and Zn, their oral bioaccessibilities, non-carcinogenic and carcinogenic health risks to children, and lead isotopic composition. The mean metal concentrations in urban soils (0.29, 36.1, 0.13, 30.9 and 113mg/kg for Cd, Cu, Hg, Pb and Zn, respectively) were about two times higher compared with background soil concentrations. The order of bioaccessible metal fractions determined by Simple Bioaccessibility Extraction Test was: Pb (59.9%) > Cu (43.8%) > Cd (40.8%) > Zn (33.6%) > Hg (12.8%). Variations in the bioaccessible metal fractions were mainly related to the total metal concentrations in urban soils. A relatively wide range of lead isotopic ratios in urban soils (1.1598-1.2088 for 206 Pb/ 207 Pb isotopic ratio) indicated a combination of anthropogenic and geogenic sources of metals in the soils. Lower values of 206 Pb/ 207 Pb isotopic ratio in the city centre and similar spatial distribution of total metal concentrations, together with their increasing total concentrations in soils towards the city centre, showed that traffic and coal combustion in former times were likely the major sources of soil contamination. The non-carcinogenic and carcinogenic health risks to children due to exposure to metals in kindergarten and urban park soils were low, with hazard index and cancer risk values below the threshold values at all studied sites. Copyright © 2017 Elsevier Inc. All rights reserved.

PSMA-Targeted Nano-Conjugates as Dual-Modality (MRI/PET) Imaging Probes for the Noninvasive Detection of Prostate Cancer

DTIC Science & Technology

2006-10-01

availability of 64Cu and 177Lu, we tried to incorporate these two isotopes to the iron oxide core of the dextran-coated nanoparticles besides arsenic...isotopes. The decay characteristics of 64Cu and 177Lu are summarized in Table 2. Table 2. Decay Characteristics of 64Cu and 177Lu. Isotope t1/2 β...MeV (%) β+ MeV (%) EC (%) γ MeV (%) 64Cu 12.7 h 0.578 (39%) 0.653 (17.4%) 41% 1.35 (0.6%) 0.511 (38.6%) 177Lu 6.71 d 0.497 (78.7%) 0.208 (11.0

In situ strontium and sulfur isotope investigation of the Ni-Cu-(PGE) sulfide ore-bearing Kevitsa intrusion, northern Finland

NASA Astrophysics Data System (ADS)

Luolavirta, Kirsi; Hanski, Eero; Maier, Wolfgang; Lahaye, Yann; O'Brien, Hugh; Santaguida, Frank

2018-01-01

The 2.06-Ga Kevitsa mafic-ultramafic intrusion in northern Finland hosts a large disseminated Ni-Cu-PGE deposit. The deposit occurs in the ultramafic olivine-pyroxene cumulates and shows a range in Ni tenors varying from 4-7 wt% (regular ore) to > 10 wt% (Ni-PGE ore). There are also a metal-poor sulfide mineralization (false ore) and contact mineralization that are uneconomic (Ni tenor < 4 wt%). The obtained 87Sr/86Sr(i) values of the Kevitsa ultramafic cumulates are highly radiogenic (> 0.7045) in comparison to the estimated depleted mantle Sr isotope ratio of 0.702 at 2.06 Ga. The sulfur δ 34S values are generally higher than + 2‰, which together with the Sr isotope data imply involvement of crustal material in the genesis of the Kevitsa intrusion and its ores. The 87Sr/86Sr(i) values obtained from the ore-bearing domain of the intrusion show stratigraphic variation and exceed 0.7050, with the maximum value reaching up to 0.7109. In contrast, in rocks around the ore domain, the initial Sr isotope compositions remain more or less constant (0.7047-0.7060) throughout the intrusive stratigraphy. The isotope data suggest that the ore-bearing domain of the intrusion represents a dynamic site with multiple injections of variably contaminated magma, whereas the surrounding part of the intrusion experienced a less vigorous emplacement history. No correlation is observed between the strontium and sulfur isotope compositions. This is explained by bulk assimilation of the silicate magma in a deeper staging magma chamber and variable assimilation of sulfur during magma transport into the Kevitsa magma chamber. The low level of metals in false ore and the Ni-depleted nature of its olivine suggest that some sulfides may have precipitated and deposited in the feeder conduit during the initial stage of magma emplacement. Cannibalization of early-formed sulfides by later magma injections may have been important in the formation of the economic ore deposit.

Interplay of crystal fractionation, sulfide saturation and oxygen fugacity on the iron isotope composition of arc lavas: An example from the Marianas

NASA Astrophysics Data System (ADS)

Williams, H. M.; Prytulak, J.; Woodhead, J. D.; Kelley, K. A.; Brounce, M.; Plank, T.

2018-04-01

Subduction zone systems are central to a multitude of processes from the evolution of the continental crust to the concentration of metals into economically viable deposits. The interplay between oxygen fugacity, sulfur saturation, fluid exsolution and fractionating mineral assemblages that gives rise to typical arc magma chemical signatures is, however, still poorly understood and novel geochemical approaches are required to make further progress. Here we examine a well-characterized suite of arc lavas from the Marianas (W. Pacific) for their stable Fe isotope composition. In agreement with previous work and mass balance considerations, contributions from sediments and/or fluids are shown to have negligible effect on Fe isotopes. Instead, we focus on disentangling processes occurring during basalt through dacite differentiation using a sample suite from the island of Anatahan. Anatahan whole rock Fe isotope compositions (δ57Fe) range from -0.05 ± 0.05 to 0.17 ± 0.03 (2 S.D.)‰. A fractionation model is constructed, where three distinct stages of differentiation are required to satisfy the combined major and trace element and isotopic observations. In particular, the sequestration of isotopically heavy Fe into magnetite and isotopically light Fe into sulfide melts yields important constraints. The data require that lavas are first undersaturated with respect to crystalline or molten sulfide, followed by the crystallisation of magnetite, which then triggers late sulfide saturation. The model demonstrates that the final stage of removal of liquid or crystalline sulfide can effectively sequester Cu (and presumably other chalcophiles) and that late stage exsolution of magmatic fluids or brines may not be required to do this, although these processes are not mutually exclusive. Finally, the new Fe isotope data are combined with previous Tl-Mo-V stable isotope determinations on the same samples. Importantly, the multi-valent transition metal stable isotope systems of Fe and V are decoupled by sulfide saturation, thus providing a potential tool to constrain its somewhat intractable timing. The observed decoupling of notionally redox-sensitive tracers underlines the caution required in the application of transition metal isotopes as direct redox proxies.

Use of Zn isotopes as a probe of anthropogenic contamination and biogeochemical processes in the Seine River, France

NASA Astrophysics Data System (ADS)

Chen, J.; Gaillardet, J.; Louvat, P.; Birck, J.

2009-05-01

Metal contamination is a major issue of human impact on the aqueous environment. River water is particularly susceptible to contamination for both dissolved and particulate loads, displaying a major challenge in understanding the dominant sources and pathways of metals in polluted drainage basins. Recent improvements in mass spectrometry allow isotopic measurements of "non-traditional" metals (Zn, Cu, Fe, etc.), making their isotopes a new potential device to investigate contamination of metals under dissolved and particulate forms in rivers. We focus here on Zn isotope geochemistry in the largely anthropized Seine River (France). A new protocol of two-column separation of Zn from dilute aqueous solution has been developed and proven to be reproducible and satisfactory for accurate measurement of Zn isotopic ratios in water samples by MC-ICP-MS (2σ = 0.04‰). Preliminary results show a total variation of 0.65‰ for δ66Zn in dissolved phases of the Seine basin, and a light isotope enrichment in anthropogenic sources compared to other water samples. The determined conservative behavior of Zn in river water makes its isotopes an effective probe of anthropogenic contamination. The natural and anthropogenic inputs were clearly identified and calculated based on Zn isotope compositions for dissolved loads. Suspended particular matters (SPM) display different Zn isotope compositions compared to dissolved loads, with a total δ66Zn variation of 0.22‰. Zn concentrations and its isotope compositions in SPM reveal inverse relationships as function of the distance from the headwater and the SPM content for geographical and temporal samples, respectively. The δ66Zn data in SPM are interpreted as reflecting the mixture of natural and anthropogenic particles. The correlation between dissolved and particulate δ66Zn shows that adsorption processes are not the dominant process making Zn enrichment in SPM. We report here for the first time systematic δ66Zn data in waters of a whole river basin, showing Zn isotopes a powerful probe to trace contamination sources and biogeochemical processes in hydrologic systems.

Controls on the Transition Metal Isotopic Composition of Seawater: Diatom Culture Experiments

NASA Astrophysics Data System (ADS)

Vance, D.; Archer, C.; Kennaway, G.; Cox, E.; Statham, P. J.

2004-12-01

Many transition metals are essential micronutrients for marine phytoplankton. As a result the expectation is that biological processes play an important, perhaps a dominant, role in their marine isotope geochemistry. These observations raise the prospect of using isotope records to trace transition metal micronutrient usage in the past oceans, an issue that is of importance to the efficiency of the biological pump and atmospheric carbon dioxide. As such, the characterisation of trace metal isotopic fractionations associated with marine primary productivity are an important scientific goal. Here we report fractionations associated with Fe, Cu and Zn sequestration by diatoms, one of the main primary producers in the oceans. Axenic unialgal cultures of Thalassiosira weissflogii and Thalassiosira pseudonana were established in artificial seawater + F/2 medium at 18° C on a 16:8 light:dark cycle. The cultures were filtered to separate diatom material from residual media and analysed for Zn, Cu and Fe concentrations and isotope composition using techniques described elsewhere1,2. Aliquots of the starting medium were also measured for each batch of cultures. The diatom organic material shows small, but consistent and resolvable, positive fractionations (0.1-0.3 per mil) for Fe, Cu and Zn relative to the starting medium. In the case of all three metals, but particularly for Zn (70-95% depending on experiment size), the diatoms had sequestered a large proportion of the available metal, suggesting that the fractionation factor for metal usage by the diatoms is much greater than 1.0001 to 1.0003. Time-series experiments are under way to determine the exact magnitude of the fractionation factor. The mass-balance is supported by the fact that the residual medium is around -0.4 per mil for Zn. The fact that diatoms incorporate trace metals that are isotopically heavier than the nutrient pool is a surprising result, the expectation having been that, as with carbon, the biological usage of trace metals would result in kinetic fractionations3. The positive fractionations necessitate an equilibrium process and, perhaps, active extra-cellular sequestration of trace metals. The second broader implication is that given the proposed role of diatoms in controlling the extreme depletion of Zn in open ocean surface waters, particularly in the Pacific where surface waters are have up to a factor of 250 less Zn than deep waters4, the depletion of the light isotope in surface waters and its enrichment in deep waters are predicted to be extreme. Zn, and other trace metal, isotopes may have an important role in recording this process in the past oceans. 1 C. Archer and D. Vance, 2004, J. Anal. Atom. Spectr. 19, 656-665. 2 J. Bermin, et al., 2004, this volume. 3 Pichat, S et al., 2003, Earth Planet. Sci. Lett. 210, 167-178. 4 Lohan, M.C. et al., 2002, Deep-Sea Res. II 49, 5793-5808.

PSMA-Targeted Nano-Conjugates as Dual-Modality (MRI/PET) Imaging Probes for the Non-Invasive Detection of Prostate Cancer

DTIC Science & Technology

2007-10-01

incorporation yields of 77As, 177Lu, 64Cu and 111In were comparable to the nanoparticles coated with the 64-76 KDa dextran. Specifically, the incorporation...ratios for a typical PET isotope 64Cu and 177Lu were about 50% and 73 %, respectively, with a total preparation time of 4 hours. After purification...radioisotope incorporation ratios for a typical PET isotope, 64Cu , and a SPECT isotope, 177Lu, were about 50% and 73 %, respectively, with a total

Metal isotope and density functional study of the tetracarboxylatodicopper(II) core vibrations

NASA Astrophysics Data System (ADS)

Drożdżewski, Piotr; Brożyna, Anna

2005-11-01

Vibrational spectra of tetrakis(acetato)diaquadicopper(II) complex have been deeply examined in order to provide a detailed description of dynamics of [Cu 2O 8C 4] core being a typical structural unit of most copper(II) carboxylates. Low frequency bands related to significant motions of metal atoms were detected by metal isotope substitution. Observed spectra and isotope shifts were reproduced in DFT calculations. For clear presentation of computed normal vibrations, a D 4h symmetry approximation was successfully applied. Basing on observed isotope shifts and calculation results, all skeletal vibrations have been analyzed including normal mode with the largest Cu ⋯Cu stretching amplitude assigned to Raman band at 178 cm -1.

Geochemical and isotopic study of soils and waters from an Italian contaminated site: Agro Aversano (Campania)

USGS Publications Warehouse

Bove, M.A.; Ayuso, R.A.; de Vivo, B.; Lima, A.; Albanese, S.

2011-01-01

Lead isotope applications have been widely used in recent years in environmental studies conducted on different kinds of sampled media. In the present paper, Pb isotope ratios have been used to determine the sources of metal pollution in soils and waters in the Agro Aversano area. During three different sampling phases, a total of 113 surface soils (5-20. cm), 20 samples from 2 soil profiles (0-1. m), 11 stream waters and 4 groundwaters were collected. Major element concentrations in sampled media have been analyzed by the ICP-MS technique. Surface soils (20 samples), all soil profiles and all waters have been also analyzed for Pb isotope compositions by thermal ionization (TIMS). The geochemical data were assessed using statistic methods and cartographically elaborated in order to have a clear picture of the level of disturbance of the area. Pb isotopic data were studied to discriminate between anthropogenic and geologic sources. Our results show that As (5.6-25.6. mg/kg), Cu (9-677. mg/kg), Pb (22-193. mg/kg), Tl (0.53-3.62. mg/kg), V (26-142. mg/kg) and Zn (34-215. mg//kg) contents in analyzed soils, exceed the intervention limits fixed by the Italian Environmental Law for residential areas in some of the sampled sites, while intervention limit for industrial areas is exceeded only for Cu concentrations. Lead isotopic data, show that there is a high similarity between the ratios measured in the leached soil samples and those deriving from anthropic activities. This similarity with anthropogenic Pb is also evident in the ratios measured in both groundwater and stream water samples. ?? 2010 Elsevier B.V.

Stable isotope tracing of Ni and Cu pollution in North-East Norway: Potentials and drawbacks.

PubMed

Šillerová, Hana; Chrastný, Vladislav; Vítková, Martina; Francová, Anna; Jehlička, Jan; Gutsch, Marissa R; Kocourková, Jana; Aspholm, Paul E; Nilsson, Lars O; Berglen, Tore F; Jensen, Henning K B; Komárek, Michael

2017-09-01

The use of Ni and Cu isotopes for tracing contamination sources in the environment remains a challenging task due to the limited information about the influence of various biogeochemical processes influencing stable isotope fractionation. This work focuses on a relatively simple system in north-east Norway with two possible endmembers (smelter-bedrock) and various environmental samples (snow, soil, lichens, PM 10 ). In general, the whole area is enriched in heavy Ni and Cu isotopes highlighting the impact of the smelting activity. However, the environmental samples exhibit a large range of δ 60 Ni (-0.01 ± 0.03‰ to 1.71 ± 0.02‰) and δ 65 Cu (-0.06 ± 0.06‰ to -3.94 ± 0.3‰) values which exceeds the range of δ 60 Ni and δ 65 Cu values determined in the smelter, i.e. in feeding material and slag (δ 60 Ni from 0.56 ± 0.06‰ to 1.00 ± 0.06‰ and δ 65 Cu from -1.67 ± 0.04‰ to -1.68 ± 0.15‰). The shift toward heavier Ni and Cu δ values was the most significant in organic rich topsoil samples in the case of Ni (δ 60 Ni up to 1.71 ± 0.02‰) and in lichens and snow in the case of Cu (δ 65 Cu up to -0.06 ± 0.06‰ and -0.24 ± 0.04‰, respectively). These data suggest an important biological and biochemical fractionation (microorganisms and/or metal uptake by higher plants, organo-complexation etc.) of Ni and Cu isotopes, which should be quantified separately for each process and taken into account when using the stable isotopes for tracing contamination in the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Development of routines for simultaneous in situ chemical composition and stable Si isotope ratio analysis by femtosecond laser ablation inductively coupled plasma mass spectrometry.

PubMed

Frick, Daniel A; Schuessler, Jan A; von Blanckenburg, Friedhelm

2016-09-28

Stable metal (e.g. Li, Mg, Ca, Fe, Cu, Zn, and Mo) and metalloid (B, Si, Ge) isotope ratio systems have emerged as geochemical tracers to fingerprint distinct physicochemical reactions. These systems are relevant to many Earth Science questions. The benefit of in situ microscale analysis using laser ablation (LA) over bulk sample analysis is to use the spatial context of different phases in the solid sample to disclose the processes that govern their chemical and isotopic compositions. However, there is a lack of in situ analytical routines to obtain a samples' stable isotope ratio together with its chemical composition. Here, we evaluate two novel analytical routines for the simultaneous determination of the chemical and Si stable isotope composition (δ(30)Si) on the micrometre scale in geological samples. In both routines, multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is combined with femtosecond-LA, where stable isotope ratios are corrected for mass bias using standard-sample-bracketing with matrix-independent calibration. The first method is based on laser ablation split stream (LASS), where the laser aerosol is split and introduced simultaneously into both the MC-ICP-MS and a quadrupole ICP-MS. The second method is based on optical emission spectroscopy using direct observation of the MC-ICP-MS plasma (LA-MC-ICP-MS|OES). Both methods are evaluated using international geological reference materials. Accurate and precise Si isotope ratios were obtained with an uncertainty typically better than 0.23‰, 2SD, δ(30)Si. With both methods major element concentrations (e.g., Na, Al, Si, Mg, Ca) can be simultaneously determined. However, LASS-ICP-MS is superior over LA-MC-ICP-MS|OES, which is limited by its lower sensitivity. Moreover, LASS-ICP-MS offers trace element analysis down to the μg g(-1)-range for more than 28 elements due to lower limits of detection, and with typical uncertainties better than 15%. For in situ simultaneous stable isotope measurement and chemical composition analysis LASS-ICP-MS in combination with MC-ICP-MS is the method of choice. Copyright © 2016 Elsevier B.V. All rights reserved.

Fontinalis antipyretica as a bioindicator of environmental conditions in freshwater ecosystem from Sava River watershed and Cerknişko Lake, Slovenia

NASA Astrophysics Data System (ADS)

Kanduč, Tjaša; Mechora, Špela; Stibilj, Vekoslava

2014-05-01

Polluted waters recharging from agriculture water systems into watersheds have influence on water quality and living habitat. Stable isotopes of carbon and nitrogen in combination with other minor and trace elements are often used to trace biogeochemical processes and contamination of water systems. The aim of the study was to assess state of environment with minor and trace elements and stable isotopes of C and N in selected Slovenian streams. Ten locations in Notranjska region, Slovenia, with different land use in the catchment (town, village, agricultural areas, farms, dairy farms), including reference point considered as non-polluted site, were sampled. Samples of water and aquatic moss F. antipyretica in Slovenian fresh waters were taken in all four seasons during years 2010 and 2012, but for stable isotope analyses of C and N only in three seasons during years 2010 and 2011. The water chemistry of investigated locations is dominated by hydrogen carbonate - calcium - magnesium, concentrations of nitrate seasonally range from 2.07 mg/l to 6.4 mg/l and at reference site does not exceed 1.3 mg/l. Total alkalinity of water at investigated locations ranges from 2.9 to 6.02 mM. The pH of investigated water range from 7.2 to 8.5, waters are saturated with oxygen (up to 134%) and conductivity ranges from 295 to 525 mikroS/cm, while at reference site conductivity is up to 180 mikroS/cm. The content of minor and trace elements in F. antipyretica ranged for Ni 4-38 mikrog/g, Zn 17-105 mikrog/g, Pb 2-28 mikrog/g, Cd 220-1953 ng/g, Cu 4-27 mikrog/g, Cr 4-49 mikrog/g, As 1-6 mikrog/g and Se 0.33-3.24 mikrog/g. The most polluted watershed was Pšata stream (agricultural areas, cattle farm) with highest values for Ni, Cr, Pb, Zn and As. The highest content of Se, was found in village (dairy farms) in Žerovniščica stream. The highest values were measured in February and October. Isotopic composition of dissolved inorganic carbon seasonally range from -13.3 to -8.1‰, and indicate waters dominated by degradation of organic matter and dissolution of carbonates. At the reference point average measured isotopic composition of dissolved inorganic carbon value is -2.7‰ which confirmed that this is a non-polluted site. Isotopic composition of carbon of F. antipyretica seasonally ranges from -45 to -32.9‰ and isotopic composition of nitrogen from -0.2‰ to 6.5‰, respectively. In comparison to C3 terrestrial plants F. antipyretica has more negative isotopic composition of carbon value, which is probably related with the difference in CO2 plant fixation and depends on isotopic composition of dissolved inorganic carbon in water, which is primarily controlled by geological composition and soil thickness in the watershed. Higher isotopic composition of nitrogen value found in F. antipyretica is related to agricultural activity in watershed, while at the reference site measured isotopic composition of nitrogen value is -4.1 ‰. From our study it is evident that isotopic composition of carbon and nitrogen is useful tracer of natural and anthropogenic inputs from terrestrial (fertilizing, sewage sludge) to water system.

Noble Gas Isotope Evidence for Mantle Volatiles in the Cu-Mo Porphyry and Main Stage Polymetallic Veins at Butte, Montana

NASA Astrophysics Data System (ADS)

Hofstra, A. H.; Rusk, B. G.; Manning, A. H.; Hunt, A. G.; Landis, G. P.

2017-12-01

Recent studies suggest that volatiles released from mafic intrusions may be important sources of heat, sulfur, and metals in porphyry Cu-Mo-Au and epithermal Au-Ag deposits associated with intermediate to silicic stocks. The huge Cu-Mo porphyry and Main Stage polymetallic vein deposits at Butte are well suited to test this hypothesis because there is no geologic or isotopic evidence of basaltic intrusions in the mine or drill holes. The Butte porphyry-vein system is associated with quartz monzonite stocks and dikes within the southwest part of the Late Cretaceous Boulder batholith. The Boulder batholith was emplaced into Mesoproterozoic to Mesozoic sedimentary rocks and Late Cretaceous volcanic rocks. The Boulder batholith and Butte intrusions have Sri and eNd values indicative of crustal contamination. Eu and Ce anomalies in zircon from Butte intrusions provide evidence of oxidation due to magma degassing. To ascertain the source of volatiles in this system, 11 samples from the Cu-Mo porphyry and 16 from Main Stage veins were selected. The isotopic composition of Ar, Ne, and He extracted from fluid inclusions in quartz, magnetite, pyrite, chalcopyrite, sphalerite, galena, enargite, and covellite were determined. Helium isotopes exceed blank levels in all samples and Ne and Ar in some samples. On a 38Ar/36Ar vs. 40Ar/36Ar diagram, data plot near air. On a 20Ne/22Ne vs. 21Ne/22Ne diagram, data extend from air along the trajectories of OIB and MORB. On a 36Ar/4He vs. 3He/4He RA diagram, data extend from crust toward the air-mantle mixing line. The maximum 3He/4He RA values in the Cu-Mo porphyry (2.86) and Main Stage veins (3.46) are from pyrite and these values correspond to 36 and 43 % mantle helium. The Ne and He results show that fluid inclusions contain volatiles discharged from mantle magmas and that these volatiles were diluted by groundwater containing He derived from country rocks. Despite the lack of mafic intrusions in the Butte magmatic center, noble gas isotopes show that volatiles derived from concealed mafic intrusions were present in the hydrothermal system. Discharge of hot volatiles from mafic magma chambers at depth may be required to prevent the overlying magma column from quenching and, thus, allow for the repeated buildup and release of sulfur- and metal-bearing fluids from apical intrusions.

Tectono-magmatic evolution of the Chihuahua-Sinaloa border region in northern Mexico: Insights from zircon-apatite U-Pb geochronology, zircon Hf isotope composition and geochemistry of granodiorite intrusions

NASA Astrophysics Data System (ADS)

Mahar, Munazzam Ali; Goodell, Philip C.; Feinstein, Michael Nicholas

2016-11-01

We present the whole-rock geochemistry, LA-ICP-MS zircon-apatite U-Pb ages and zircon Hf isotope composition of the granodioritic plutons at the southwestern boundary of Chihuahua with the states of Sinaloa and Sonora. These granodiorites are exposed in the north and south of the Rio El Fuerte in southwest Chihuahua and northern Sinaloa. The magmatism spans over a time period of 37 Ma from 90 to 53 Ma. Zircons are exclusively magmatic with strong oscillatory zoning. No inheritance of any age has been observed. Our new U-Pb dating ( 250 analyses) does not support the involvement of older basement lithologies in the generation of the granitic magmas. The U-Pb apatite ages from granodiorites in southwest Chihuahua vary from 52 to 70 Ma. These apatite ages are 1 to 20 Ma younger than the corresponding zircon U-Pb crystallization ages, suggesting variable cooling rates from very fast to 15 °C/Ma ( 800 °C to 500 °C) and shallow to moderate emplacement depths. In contrast, U-Pb apatite ages from the Sinaloa batholith are restricted from 64 to 61 Ma and are indistinguishable from the zircon U-Pb ages range from 67 to 60 Ma within the error, indicating rapid cooling and very shallow emplacement. However, one sample from El Realito showed a larger difference of 20 Ma in zircon-apatite age pair: zircon 80 ± 0.8 Ma and apatite 60.6 ± 4 Ma, suggesting a slower cooling rate of 15 °C/Ma. The weighted mean initial εHf (t) isotope composition (2σ) of granodiorites varies from + 1.8 to + 5.2. The radiogenic Hf isotope composition coupled with previous Sr-Nd isotope data demonstrates a significant shift from multiple crustal sources in the Sonoran batholithic belt to the predominant contribution of the mantle-derived magmas in the southwest Chihuahua and northern Sinaloa. Based on U-Pb ages, the absence of inheritance, typical high Th/U ratio and radiogenic Hf isotope composition, we suggest that the Late Cretaceous-Paleogene magmatic rocks in this region are not derived from melting of a felsic older crust, neither evolved North American Proterozoic basement nor Jurassic metasedimentary rocks of the Guerrero terrane. Instead, the magma was primarily derived from partial melting of mantle related sources, possibly in the subcontinental mantle wedge above the Farallon plate. Our younger U-Pb zircon-apatite ages are well correlated with the late-stage cogenetic porphyry Cu-Au mineralization at 57 to 59 Ma. If the origin of ore mineralization is related to the magma sources of host batholiths, then a minimal input from crustal melt is suggested in the genesis of Cu-Au porphyry system.

High-Speed, Three Dimensional Object Composition Mapping Technology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ishikawa, M Y

2001-02-14

This document overviews an entirely new approach to determining the composition--the chemical-elemental, isotopic and molecular make-up--of complex, highly structured objects, moreover with microscopic spatial resolution in all 3 dimensions. The front cover depicts the new type of pulsed laser system at the heart of this novel technology under adjustment by Alexis Wynne, and schematically indicates two of its early uses: swiftly analyzing the 3-D composition governed structure of a transistor circuit with both optical and mass-spectrometric detectors, and of fossilized dinosaur and turtle bones high-speed probed by optical detection means. Studying the composition-cued 3-D micro-structures of advanced composite materials andmore » the microscopic scale composition-texture of biological tissues are two near-term examples of the rich spectrum of novel applications enabled by this field-opening analytic tool-set.« less

Genesis of the Assif El Mal Zn-Pb (Cu, Ag) vein deposit. An extension-related Mesozoic vein system in the High Atlas of Morocco. Structural, mineralogical, and geochemical evidence

USGS Publications Warehouse

Bouabdellah, M.; Beaudoin, G.; Leach, D.L.; Grandia, F.; Cardellach, E.

2009-01-01

The Assif El Mal Zn-Pb (Cu-Ag) vein system, located in the northern flank of the High Atlas of Marrakech (Morocco), is hosted in a Cambro-Ordovician volcaniclastic and metasedimentary sequence composed of graywacke, siltstone, pelite, and shale interlayered with minor tuff and mudstone. Intrusion of synorogenic to postorogenic Late Hercynian peraluminous granitoids has contact metamorphosed the host rocks giving rise to a metamorphic assemblage of quartz, plagioclase, biotite, muscovite, chlorite, amphibole, chloritoid, and garnet. The Assif El Mal Zn-Pb (Cu-Ag) mineralization forms subvertical veins with ribbon, fault breccia, cockade, comb, and crack and seal textures. Two-phase liquid-vapor fluid inclusions that were trapped during several stages occur in quartz and sphalerite. Primary inclusion fluids exhibit Th mean values ranging from 104??C to 198??C. Final ice-melting temperatures range from -8.1??C to -12.8??C, corresponding to salinities of ???15 wt.% NaCl equiv. Halogen data suggest that the salinity of the ore fluids was largely due to evaporation of seawater. Late secondary fluid inclusions have either Ca-rich, saline (26 wt.% NaCl equiv.), or very dilute (3.5 wt.% NaCl equiv.) compositions and homogenization temperatures ranging from 75??C to 150??C. The ??18O and ??D fluid values suggest an isotopically heterogeneous fluid source involving mixing between connate seawater and black-shale-derived organic waters. Low ??13CVPDB values ranging from -7.5??? to -7.7??? indicate a homogeneous carbon source, possibly organic matter disseminated in black shale hosting the Zn-Pb (Cu-Ag) veins. The calculated ??34SH2S values for reduced sulfur (22.5??? to 24.3???) are most likely from reduction of SO42- in trapped seawater sulfate or evaporite in the host rocks. Reduction of sulfate probably occurred through thermochemical sulfate reduction in which organic matter was oxidized to produce CO2 which ultimately led to precipitation of saddle dolomite with isotopically light carbon. Lead isotope compositions are consistent with fluid-rock interaction that leached metals from the immediate Cambro-Ordovician volcaniclastic and metasedimentary sequence or from the underlying Paleo-Neoproterozoic crustal basement. Geological constraints suggest that the vein system of Assif El Mal formed during the Jurassic opening of the central Atlantic Ocean. ?? Springer-Verlag 2009.

Using lead isotopes and trace element records from two contrasting Lake Tanganyika sediment cores to assess watershed – Lake exchange

USGS Publications Warehouse

Odigie, Kingsley; Cohen, A.D.; Swarzenski, Peter W.; Flegal, R

2014-01-01

Lead isotopic and trace element records of two contrasting sediment cores were examined to reconstruct historic, industrial contaminant inputs to Lake Tanganyika, Africa. Observed fluxes of Co, Cu, Mn, Ni, Pb, and Zn in age-dated sediments collected from the lake varied both spatially and temporally over the past two to four centuries. The fluxes of trace elements were lower (up to 10-fold) at a mid-lake site (MC1) than at a nearshore site (LT-98-58), which is directly downstream from the Kahama and Nyasanga River watersheds and adjacent to the relatively pristine Gombe Stream National Park. Trace element fluxes at that nearshore site did not measurably change over the last two centuries (1815–1998), while the distal, mid-lake site exhibited substantial changes in the fluxes of trace elements – likely caused by changes in land use – over that period. For example, the flux of Pb increased by ∼300% from 1871 to 1991. That apparent accelerated weathering and detrital mobilization of lithogenic trace elements was further evidenced by (i) positive correlations (r = 0.77–0.99, p < 0.05) between the fluxes of Co, Cu, Mn, Ni, Pb, and Zn and those of iron (Fe) at both sites, (ii) positive correlations (r = 0.82–0.98, p < 0.01, n = 9) between the fluxes of elements (Al, Co, Cu, Fe, Mn, Ni, Pb, and Zn) and the mass accumulation rates at the offshore site, (iii) the low enrichment factors (EF < 5) of those trace elements, and (iv) the temporal consistencies of the isotopic composition of Pb in the sediment. These measurements indicate that accelerated weathering, rather than industrialization, accounts for most of the increases in trace element fluxes to Lake Tanganyika in spite of the development of mining and smelting operations within the lake’s watershed over the past century. The data also indicate that the mid-lake site is a much more sensitive and useful recorder of environmental changes than the nearshore site. Furthermore, the lead isotopic compositions of sediment at the sites differed spatially, indicating that the Pb (and other trace elements by association) originated from different natural sources at the two locations.

Possible Mesozoic age of Ellenville Zn-Pb-Cu(Ag) deposit, Shawangunk Mountains, New York

USGS Publications Warehouse

Friedman, J.D.; Conrad, J.E.; McKee, E.H.; Mutschler, F.E.; Zartman, R.E.

1994-01-01

Ore textures, epithermal open-space filling of Permian structures of the Alleghanian orogeny, and largely postorogenic mineralization of the Ellenville, New York, composite Zn-Pb-Cu(Ag) vein system, provide permissive evidence for post-Permian mineralization. Isochron ages determined by 40Ar/39Ar laser-fusion techniques for K-bearing liquid inclusions in main-stage quartz from the Ellenville deposit additionally suggest a Mesozoic time of mineralization, associated with extensional formation of the Newark basin. The best 40Ar/39Ar total-fusion age range is 165 ?? 30 to 193 ?? 35 Ma. The Mesozoic 40Ar/39Ar age agrees with that of many other dated northern Appalachian Zn-Pb-Cu(Ag) deposits with near-matching lead isotope ratios, and adds new evidence of Jurassic tectonism and mineralization as an overprint to Late Paleozoic tectonism at least as far north as Ellenville (lat. 41??43???N). ?? 1994 Springer-Verlag.

Iron Isotopes in Meteorites

NASA Astrophysics Data System (ADS)

Kehm, K.; Alexander, C. M.; Hauri, E. H.

2001-12-01

The recent identification of naturally occurring isotopic mass fractionation of the transition met-als on the Earth has prompted a search for similar variability in meteorites. Studies of Cu, Zn, and Fe, for example, have revealed per-mil level and larger mass fractionations between different bulk meteorites. Such variations can result from temperature-sensitive isotope exchange reactions and kinetic processes, and therefore may reflect conditions in the solar nebula and on meteorite parent bodies. Recent advances in ICP-MS have permitted isotope studies of transition metals and other elements with similarly small isotopic mass dispersions. Among the transition metals, Fe is perhaps the most difficult to analyze by ICP-MS because plasma sources are copious producers of argide molecules that interfere with the measurement of iron isotopes. However, the stable isotope behavior of Fe is of special interest because it is a non-refractory major element in meteorites, present in a variety of mineral associations and redox states. Considerable effort has gone into overcoming the inherent analytical difficulties of measuring Fe using ICP-MS. We recently reported on a technique that achieves argide reduction by operating the plasma source in so-called 'cold' mode. In this presentation, we report results from this ongoing work. To date, analyses of nine different meteorites, and eight individual Tieschitz (H3) chondrules have been completed, along with a number of measurements of the Hawaiian basalt sample Kil1919. All of the bulk meteorite compositions, which include both chondrites and irons, have identical 56Fe/54Fe to within ~ 0.14 per mil (2 sigma), and are indistinguishable from the composition of the terrestrial basalt. The Tieschitz chondrules, on the other hand, tend to have isotopically light compositions. This could reflect formation from fractionated starting material. Alternatively, Fe condensation, under non-equilibrium conditions can enrich light isotopes. Future work will focus on determining the extent of Fe mass fractionation in chondrules from Tieschitz as well as other chondrites. This growing database will help us to understand the conditions in which chondrules formed, potentially placing stringent constraints on theories of their formation.

In-situ Pb isotope analysis of Fe-Ni-Cu sulphides by laser ablation multi-collector ICPMS: New insights into ore formation in the Sudbury impact melt sheet

NASA Astrophysics Data System (ADS)

Darling, J. R.; Storey, C. D.; Hawkesworth, C. J.; Lightfoot, P. C.

2012-12-01

Laser-ablation (LA) multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) is ideally suited to in situ determination of isotope ratios in sulphide minerals. Using samples of magmatic sulphide ore from the Sudbury impact structure, we test LA-MC-ICPMS analytical protocols that aim to meet a range of analytical challenges in the analysis of Pb isotopes. These include: potential matrix sensitive isotopic fractionation; interferences on Pb isotopes; low melting points of many sulphide minerals; the availability of standards. Magmatic sulphides of wide ranging mineralogy (pyrrhotite, pentlandite, chalcopyrite, pyrite and sphalerite) were analysed for Pb isotopic composition, using the silicate glass NIST SRM 610 as an external standard to correct for instrumental mass-fractionation. Despite matrix sensitive melting and re-deposition around ablation pits, several lines of evidence indicate that all analyses are accurate, within typical analytical uncertainties of 0.003-2% (2σ), and that the defined approach is insensitive to compositional diversity in sample matrix: (a) laser ablation and dissolution based measurements of sulphide powders are in agreement; (b) analyses from each sample define isochron ages within uncertainty of the known crystallization age (1850 Ma); (c) the results of sulphide measurements by laser ablation are consistent with age-corrected feldspar analyses from the same samples. The results have important implications for ore formation in Sudbury. The Pb isotope data regressions are consistent with age corrected feldspar analyses from each respective sample, which together with time integrated Th/U ratios that match whole rock values (3.1, 4.0 and 6.1 for the Worthington, Copper Cliff and Parkin Offset Dykes, respectively) indicate chemical equilibrium between the silicate and sulphide systems during ore formation. The sulphides within each respective sample have indistinguishable model initial Pb isotope ratios (207Pb/204Pbm), irrespective of mineralogy or texture, indicating a common origin for ores within each of three different Offset Dykes. Furthermore, variations between Offset Dykes (e.g., 207Pb/204Pbm = 15.514 ± 0.012, 15.399 ± 0.009 and 15.275 ± 0.003) show that the ores have differing crustal sources on previously unrecognized scales. Mass balance considerations, particularly for MgO, Ni and Cu, indicate that the spatial distribution of mafic target rocks played a significant role in controlling the mineralization potential in different parts of the melt sheet.

Spatial and ontogenetic variability in the chemical composition of juvenile common sole ( Solea solea) otoliths

NASA Astrophysics Data System (ADS)

Tanner, S. E.; Vasconcelos, R. P.; Reis-Santos, P.; Cabral, H. N.; Thorrold, S. R.

2011-01-01

A description of variations in the chemical composition of fish otoliths at different spatial scales and life history stages is a prerequisite for their use as natural tags in fish population connectivity and migration studies. Otolith geochemistry of juvenile common sole ( Solea solea), a marine migrant species collected in six Portuguese estuaries was examined. Elemental ratios (Mg:Ca, Mn:Ca, Cu:Ca, Sr:Ca, Ba:Ca, Pb:Ca) were analysed in two zones of the right otolith (corresponding to late larval and juvenile stages) using laser ablation inductively coupled plasma mass spectrometry (ICP-MS). Stable carbon and oxygen isotopes (δ 13C and δ 18O) were determined in left otoliths using isotopic ratio monitoring mass spectrometry (irm-MS). Significant differences in otolith geochemical signatures were found among estuaries, among sites within estuaries and between otolith zones. Several elemental ratios (Mg:Ca, Mn:Ca, Cu:Ca and Sr:Ca) showed consistent patterns between otolith zones and were likely influenced by environmental factors and ontogenetic effects associated with physiological changes during metamorphosis. Assignment of individuals to their collection estuary based on the otolith geochemical signatures was more accurate at the site level (81%) than among estuaries (69%). Site temperature was not correlated with any of the elemental or isotope ratios, but salinity was significantly correlated with Ba:Ca, δ 13C and δ 18O. Observed spatial variations among estuaries and sites within estuaries indicate that geochemical signatures in otoliths are accurate natural tags of estuarine habitat in common sole. Nevertheless, the significant variations observed between otolith zones should be taken into account in the design of population connectivity studies.

Partial-melting of fertile metasedimentary rocks controlling the ore formation in the Jiangnan porphyry-skarn tungsten belt, south China: A case study at the giant Zhuxi W-Cu skarn deposit

NASA Astrophysics Data System (ADS)

Song, Shiwei; Mao, Jingwen; Zhu, Yongfeng; Yao, Zaiyu; Chen, Guohua; Rao, Jianfeng; Ouyang, Yongpeng

2018-04-01

The Zhuxi W-Cu deposit, located in the Jiangnan porphyry-skarn W belt, is a world-class W deposit. We studied three coeval mineralization-related intrusions composed of biotite monzogranite, fine-grained granite, and granite porphyry in the Zhuxi mine. These rocks contain peritectic garnet and K-feldspar. The LA-ICP-MS U-Pb dating of zircon from the biotite monzogranite, fine-grained granite, and granite porphyry yields average ages of 149.38 ± 0.86 Ma, 149.0 ± 1.0 Ma, and 148.30 ± 1.4 Ma, respectively. The Zhuxi granites are enriched in Cs, Rb, and U and depleted in Ba, Sr, and Ti, with ASI [molar Al2O3 / (CaO + Na2O + K2O)] values of 1.03-2.15. The fine-grained granite exhibits initial 87Sr/86Sr values of 0.716-0.717 and εNd(t) values ranging from -9.61 to -9.21. The εHf(t) values of the biotite monzogranite and fine-grained granite range from -8.83 to -6.30 and from -9.86 to -7.62, respectively. The Sr-Nd-Hf isotopic compositions of these rocks are similar to those of the fertile Neoproterozoic metasedimentary rocks in the Jiangnan W belt. The Zhuxi granites are S-type granites based on their mineral assemblages and geochemical characteristics. The Hf isotopic compositions, Sr-Nd isotopic characteristics, and trace element modelling suggest that the studied granites formed from the dehydration melting of fertile Neoproterozoic metasedimentary rocks caused by the Late Jurassic underplating of OIB-like basaltic magma.

Oxygen isotope effect in YBa2Cu3O7 prepared by burning YBa2Cu3 in 16O and 18O

NASA Astrophysics Data System (ADS)

Yvon, Pascal J.; Schwarz, R. B.; Pierce, C. B.; Bernardez, L.; Conners, A.; Meisenheimer, R.

1989-04-01

We prepared YBa2Cu3 powder by ball milling a 2:1 molar mixture of the intermetallics BaCu and CuY. We synthesized YBa2Cu3(16O)7-x and YBa2Cu3(18O)7-x by oxidizing the YBa2Cu3 powder in 16O and 18O. The 16O/18O ratios were determined by laser-ionization and sputtering-ionization mass spectroscopy. The YBa2Cu3(160)7-x sample had 99.8 at. %16O, and the YBa2Cu3(18O)7-x sample had 96.5 at. %18O. Susceptibility measurements of the superconducting transition temperature (Tc=91.7 K for 16O; half-point transition at 84 K show an isotope effect of 0.4+/-0.1 K.

Ages and sources of components of Zn-Pb, Cu, precious metal, and platinum group element deposits in the goodsprings district, Clark County, Nevada

USGS Publications Warehouse

Vikre, Peter G.; Browne, Quentin J.; Fleck, Robert J.; Hofstra, Albert H.; Wooden, Joseph L.

2011-01-01

The Goodsprings district, Clark County, Nevada, includes zinc-dominant carbonate replacement deposits of probable late Paleozoic age, and lead-dominant carbonate replacement deposits, copper ± precious metal-platinum group element (PGE) deposits, and gold ± silver deposits that are spatially associated with Late Triassic porphyritic intrusions. The district encompasses ~500 km2 although the distribution of all deposits has been laterally condensed by late Mesozoic crustal contraction. Zinc, Pb, and Cu production from about 90 deposits was ~160,000 metric tons (t) (Zn > Pb >> Cu), 2.1 million ounces (Moz) Ag, 0.09 Moz Au, and small amounts of PGEs—Co, V, Hg, Sb, Ni, Mo, Mn, Ir, and U—were also recovered.Zinc-dominant carbonate replacement deposits (Zn > Pb; Ag ± Cu) resemble Mississippi Valley Type (MVT) Zn-Pb deposits in that they occur in karst and fault breccias in Mississippian limestone where the southern margin of the regional late Paleozoic foreland basin adjoins Proterozoic crystalline rocks of the craton. They consist of calcite, dolomite, sphalerite, and galena with variably positive S isotope compositions (δ34S values range from 2.5–13‰), and highly radiogenic Pb isotope compositions (206Pb/204Pb >19), typical of MVT deposits above crystalline Precambrian basement. These deposits may have formed when southward flow of saline fluids, derived from basinal and older sedimentary rocks, encountered thinner strata and pinch-outs against the craton, forcing fluid mixing and mineral precipitation in karst and fault breccias. Lead-dominant carbonate replacement deposits (Pb > Zn, Ag ± Cu ± Au) occur among other deposit types, often near porphyritic intrusions. They generally contain higher concentrations of precious metals than zinc-dominant deposits and relatively abundant iron oxides after pyrite. They share characteristics with copper ± precious metal-PGE and gold ± silver deposits including fine-grained quartz replacement of carbonate minerals in ore breccias and relatively low S and Pb isotope values (δ34S values vary from 0–~4‰; 206Pb/204Pb <18.5). Copper ± precious metal-PGE deposits (Cu, Co, Ag, Au, Pd, and Pt) consist of Cu carbonate minerals (after chalcocite and chalcopyrite) and fine-grained quartz that have replaced breccia clasts and margins of fissures in Paleozoic limestones and dolomites near porphyritic intrusions. Gold ± silver deposits occur along contacts and within small-volume stocks and dikes of feldspar porphyry, one textural variety of porphyritic intrusions. Lead isotope compositions of copper ± precious metal-PGE, gold ± silver, and lead-dominant carbonate replacement deposits are similar to those of Mojave crust plutons, indicating derivation of Pb from 1.7 Ga crystalline basement or from Late Proterozoic siliciclastic sedimentary rocks derived from 1.7 Ga crystalline basement.Four texturally and modally distinctive porphyritic intrusions are exposed largely in the central part of the district: feldspar quartz porphyry, plagioclase quartz porphyry, feldspar biotite quartz porphyry, and feldspar porphyry. Intrusions consist of 64 to 70 percent SiO2 and variable K2O/Na2O (0.14–5.33) that reflect proportions of K-feldspar and albite phenocrysts and megacrysts as well as partial alteration to K-mica; quartz and biotite phenocrysts are present in several subtypes. Albite may have formed during emplacement of magma in brine-saturated basinal strata, whereas hydrothermal alteration of matrix, phenocrystic, and megacrystic feldspar and biotite to K-mica, pyrite, and other hydrothermal minerals occurred during and after intrusion emplacement. Small volumes of garnet-diopside-quartz and retrograde epidote-mica-amphibole skarn have replaced carbonate rocks adjacent to one intrusion subtype (feldspar-quartz porphyry), but alteration of carbonate rocks at intrusion contacts elsewhere is inconspicuous.Uranium-lead ages of igneous zircons vary inconsistently from ~ 180 to 230 Ma and are too imprecise to distinguish age differences among intrusion subtypes; most ages are 210 to 225 Ma, yielding a mean of 217 ± 1 Ma. K-Ar and 40Ar/39Ar ages of magmatic (plagioclase, biotite) and hydrothermal (K-mica) minerals span a similar range (183–227 Ma), demonstrating broadly contemporaneous intrusion emplacement and hydrothermal alteration but allowing for multiple Late Triassic magmatic-hydrothermal events. Imprecision and range of isotopic ages may have resulted from burial beneath Mesozoic and Tertiary strata and multiple intrusion of magmas, causing thermal disturbance to Ar systems and Pb loss from zircons in intrusions.Separate late Paleozoic (zinc-dominant carbonate replacement deposits) and Late Triassic (all other deposits) mineralizing events are supported by form, distribution, and host rocks of metal deposits, by hydrothermal mineral assemblages, isotope compositions, metal abundances, and metal diversity, and by small intrusion volumes. These characteristics collectively distinguish the Goodsprings district from larger intrusion related carbonate replacement districts in the western United States. They can be used to evaluate proximity to unexposed porphyritic intrusions associated with PGE and gold ± silver mineralization.

Effect of Wood Aging on Wine Mineral Composition and 87Sr/86Sr Isotopic Ratio.

PubMed

Kaya, Ayse D; Bruno de Sousa, Raúl; Curvelo-Garcia, António S; Ricardo-da-Silva, Jorge M; Catarino, Sofia

2017-06-14

The evolution of mineral composition and wine strontium isotopic ratio 87 Sr/ 86 Sr (Sr IR) during wood aging were investigated. A red wine was aged in stainless steel tanks with French oak staves (Quercus sessiliflora Salisb.), with three industrial scale replicates. Sampling was carried out after 30, 60, and 90 days of aging, and the wines were evaluated in terms of general analysis, phenolic composition, total polysaccharides, multielement composition, and Sr IR. Li, Be, Mg, Al, Sc, Ti, V, Mn, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Mo, Sb, Cs, Ba, Pr, Nd, Sm, Eu, Dy, Ho, Er, Yb, Lu, Tl, and Pb elements and 87 Sr/ 86 Sr were determined by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) and Na, K, Ca, and Fe by flame atomic absorption spectrometry (FAAS). Two-way ANOVA was applied to assess wood aging and time effect on Sr IR and mineral composition. Wood aging resulted in significantly higher concentrations of Mg, V, Co, Ni, and Sr. At the end of the aging period, wine exhibited statistically identical Sr IR compared to control. Study suggests that wood aging does not affect 87 Sr/ 86 Sr, not precluding the use of this parameter for wine traceability purposes.

Variation of molybdenum isotopes in molybdenite from porphyry and vein Mo deposits in the Gangdese metallogenic belt, Tibetan plateau and its implications

NASA Astrophysics Data System (ADS)

Wang, Yong; Zhou, Lian; Gao, Shan; Li, Jian-Wei; Hu, Zhi-Fang; Yang, Lu; Hu, Zhao-Chu

2016-02-01

We present Mo isotopic ratios of molybdenite from five porphyry molybdenum deposits (Chagele, Sharang, Jiru, Qulong, and Zhuonuo) and one quartz-molybdenite vein-type deposit (Jigongcun) along the Gangdese metallogenic belt in the Tibetan Plateau. These deposits represent a sequence of consecutive events of the India-Asia collision at different periods. Additional molybdenite samples from the Henderson Mo deposit (USA), the oceanic subduction-related El Teniente (Chile), and Bingham (USA) porphyry Cu-(Mo) deposits were analyzed for better understanding the controls on the Mo isotope systematics of molybdenite. The results show that molybdenite from Sharang, Jiru, Qulong, and Zhuonuo deposits have similar δ97Mo (˜0 ‰), in agreement with the values of the Henderson Mo deposit (-0.10 ‰). In contrast, samples from the Changle and Jigongcun deposit have δ97Mo of 0.85 ‰ to 0.88 ‰ and -0.48 %, respectively. Molybdenite from the El Teniente and Bingham deposits yields intermediate δ97Mo of 0.27 and 0.46 ‰, respectively. The Mo isotopes, combined with Nd isotope data of the ore-bearing porphyries, indicate that source of the ore-related magmas has fundamental effects on the Mo isotopic compositions of molybdenite. Our study indicates that molybdenite related to crustal-, and mantle-derived magmas has positive or negative δ97Mo values, respectively, whereas molybdenite from porphyries formed by crust-mantle mixing has δ97Mo close to 0 ‰. It is concluded that the Mo isotope composition in the porphyry system is a huge source signature, without relation to the tectonic setting under which the porphyry deposits formed.

Industrially synthesized single-walled carbon nanotubes: compositional data for users, environmental risk assessments, and source apportionment

NASA Astrophysics Data System (ADS)

Plata, D. L.; Gschwend, P. M.; Reddy, C. M.

2008-05-01

Commercially available single-walled carbon nanotubes (SWCNTs) contain large percentages of metal and carbonaceous impurities. These fractions influence the SWCNT physical properties and performance, yet their chemical compositions are not well defined. This lack of information also precludes accurate environmental risk assessments for specific SWCNT stocks, which emerging local legislation requires of nanomaterial manufacturers. To address these needs, we measured the elemental, molecular, and stable carbon isotope compositions of commercially available SWCNTs. As expected, catalytic metals occurred at per cent levels (1.3-29%), but purified materials also contained unexpected metals (e.g., Cu, Pb at 0.1-0.3 ppt). Nitrogen contents (up to 0.48%) were typically greater in arc-produced SWCNTs than in those derived from chemical vapor deposition. Toluene-extractable materials contributed less than 5% of the total mass of the SWCNTs. Internal standard losses during dichloromethane extractions suggested that metals are available for reductive dehalogenation reactions, ultimately resulting in the degradation of aromatic internal standards. The carbon isotope content of the extracted material suggested that SWCNTs acquired much of their carbonaceous contamination from their storage environment. Some of the SWCNTs, themselves, were highly depleted in 13C relative to petroleum-derived chemicals. The distinct carbon isotopic signatures and unique metal 'fingerprints' may be useful as environmental tracers allowing assessment of SWCNT sources to the environment.

Harvesting (67)Cu from the Collection of a Secondary Beam Cocktail at the National Superconducting Cyclotron Laboratory.

PubMed

Mastren, Tara; Pen, Aranh; Loveless, Shaun; Marquez, Bernadette V; Bollinger, Elizabeth; Marois, Boone; Hubley, Nicholas; Brown, Kyle; Morrissey, David J; Peaslee, Graham F; Lapi, Suzanne E

2015-10-20

Isotope harvesting is a promising new method to obtain isotopes for which there is no reliable continuous supply at present. To determine the possibility of obtaining radiochemically pure radioisotopes from an aqueous beam dump at a heavy-ion fragmentation facility, preliminary experiments were performed to chemically extract a copper isotope from a large mixture of projectile fragmentation products in an aqueous medium. In this work a 93 MeV/u secondary beam cocktail was collected in an aqueous beam stop at the National Superconducting Cyclotron Laboratory (NSCL) located on the Michigan State University (MSU) campus. The beam cocktail consisted of ∼2.9% (67)Cu in a large mixture of co-produced isotopes ranging in atomic number from ∼19 to 34. The chemical extraction of (67)Cu was achieved via a two-step process: primary extraction using a divalent metal chelation disk followed by anion-exchange chromatography. A significant fraction (74 ± 4%) of the (67)Cu collected in the aqueous beam stop was recovered with >99% radiochemical purity. To illustrate the utility of this product, the purified (67)Cu material was then used to radiolabel an anti-EGFR antibody, Panitumumab, and injected into mice bearing colon cancer xenografts. The tumor uptake at 5 days postinjection was found to be 12.5 ± 0.7% which was in very good agreement with previously reported studies with this radiolabeled antibody. The present results demonstrate that harvesting isotopes from a heavy-ion fragmentation facility could be a promising new method for obtaining high-quality isotopes that are not currently available by traditional methods.

Source discrimination of atmospheric metal deposition by multi-metal isotopes in the Three Gorges Reservoir region, China.

PubMed

Liu, Jinling; Bi, Xiangyang; Li, Fanglin; Wang, Pengcong; Wu, Jin

2018-05-12

Concentrations of heavy metals, as well as isotopic compositions of mercury (Hg) and lead (Pb), in mosses (Bryum argenteum) from the Three Gorges Reservoir (TGR) region were investigated to decipher the sources of atmospheric metals in this region. Higher contents of metals (0.90 ± 0.65 mg/kg of Cd, 24.6 ± 27.4 mg/kg of Cu, and 36.1 ± 51.1 mg/kg of Pb) in the mosses from TGR were found compared with those from pollution-free regions. Principal component analysis (PCA) grouped the moss metals into four main components which were associated with both anthropogenic and natural sources. The ratios of Pb isotopes of the mosses (1.153-1.173 for 206 Pb/ 207 Pb and 2.094-2.129 for 208 Pb/ 206 Pb) fell between those of the traffic emissions and coals. Similarly, the compositions of δ 202 Hg (-4.29∼-2.33‰) and Δ 199 Hg (within ±0.2‰) were comparable to those of the coals and coal combustion emissions from China and India. These joined results of Pb and Hg isotope data give solid evidences that the coal combustion and traffic emissions are the main causes of metal accumulation in the TGR region. Copyright © 2018 Elsevier Ltd. All rights reserved.

Carbon Isotope Fractionations Associated with Methanotrophic Growth with the Soluble and Particulate Methane Monooxygenases

NASA Technical Reports Server (NTRS)

Jahnke, Linda L.; Summons, Roger E.; Chang, Sherwood (Technical Monitor)

1996-01-01

Growth experiments with the RuMP-type methanotroph, Methylococcus capsulatus (Bath), have demonstrated that biomass and lipid biomarkers are significantly depleted in C-13 compared to the substrate methane and that the extent of fractionation is dependent on whether cells express the soluble (s) or particulate (p) methane monooxygenase (MMO). The presence or absence of the characteristic sMMO subunits was monitored using SDS-polyacrylamide gels. In M. capsulatus grown with no Cu supplementation, the characteristic sMMO subunits were observed in the soluble fraction throughout the entire growth period and biomass was depleted in C-13 by approximately 14,700 relative to substrate methane. In cells grown with 5uM Cu, no sMMO bands were observed and a greater fractionation of approximately 27,700 in resultant biomass was obtained. Methanol growth experiments with M. capsulatus and with a RuMP methylotroph, Methylophilus methylotrophus, in which biomass measurements yielded depletions in C-13 of 9 and 5%(sub o), respectively, suggest that oxidation of methane is the major fractionation step. Growth of M. capsulatus at a low level of oxygen, approximately 0.5%, had no significant effect on carbon isotope fractionation by either sMMO or pMMO. These observations are significant for identification of molecular biomarkers; and methanotrophic contributions to carbon isotope composition in natural environments.

Track structure simulation for positron emitters of physical interest. Part II: The case of the radiometals

NASA Astrophysics Data System (ADS)

Le Loirec, C.; Champion, C.

2007-11-01

The development of radiochemical services in hospitals, due to the wide use of Positron Emission Tomography (PET) in nuclear medicine, has led to the synthesis of new radiotracers among them radiometals which present a large panel of advantages in terms of half-life times and emission spectra. The most encouraging are the copper isotopes 62Cu and 64Cu as well as 60Cu and 61Cu and the technetium isotope 94mTc used for diagnosis and pharmacokinetic studies. The manganese isotopes 52mMn, 52Mn and 51Mn also present some interesting characteristics, especially 52mMn produced during the decay of 52Fe. Finally, the less known isotopes 89Zr, 45Ti, and 86Y can also be used as surrogates of some therapeutic agents, whereas 38K, 55Co and 66Ga may be used as PET imaging tracers. In this work, we propose an intercomparison of these PET radiometal isotopes. To do that, we have used the home-made Monte Carlo simulation previously described in Champion and Le Loirec [Phys. Med. Biol. 51 (2006) 1707] to simulate the complete decay of β + tracers in biological matter. Under these conditions, we access to a complete description of the positronic irradiation during PET exams using metallic isotopes. The results obtained are also compared with existing theoretical and experimental data and good agreement is generally observed.

First Measurement of the Radionuclide Purity of the Therapeutic Isotope 67Cu Produced by 68Zn(n,x) Reaction Using natC(d,n) Neutrons

NASA Astrophysics Data System (ADS)

Sato, Nozomi; Tsukada, Kazuaki; Watanabe, Satoshi; Ishioka, Noriko S.; Kawabata, Masako; Saeki, Hideya; Nagai, Yasuki; Kin, Tadahiro; Minato, Futoshi; Iwamoto, Nobuyuki; Iwamoto, Osamu

2014-07-01

We have for the first time studied the radionuclide purity of the therapeutic isotope 67Cu produced by the 68Zn(n,x)67Cu reaction. The neutrons were obtained by the natC(d,n) reaction using 40 MeV deuterons. We measured the γ-ray spectra of the reaction products produced by bombarding an enriched 68ZnO sample with the neutrons with a high-purity Ge detector. We found that the relative production yields of the impurity radionuclides 64Cu, 65Zn, and 69mZn to 67Cu are extremely low. The result indicates that the 68Zn(n,x)67Cu reaction is the most promising among those proposed routes until now for producing high-quality 67Cu, and could solve a longstanding problem of establishing an appropriate production method for 67Cu.

Sulfate and sulfide sulfur isotopes (δ34S and δ33S) measured by solution and laser ablation MC-ICP-MS: An enhanced approach using external correction

USGS Publications Warehouse

Pribil, Michael; Ridley, William I.; Emsbo, Poul

2015-01-01

Isotope ratio measurements using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) commonly use standard-sample bracketing with a single isotope standard for mass bias correction for elements with narrow-range isotope systems measured by MC-ICP-MS, e.g. Cu, Fe, Zn, and Hg. However, sulfur (S) isotopic composition (δ34S) in nature can range from at least − 40 to + 40‰, potentially exceeding the ability of standard-sample bracketing using a single sulfur isotope standard to accurately correct for mass bias. Isotopic fractionation via solution and laser ablation introduction was determined during sulfate sulfur (Ssulfate) isotope measurements. An external isotope calibration curve was constructed using in-house and National Institute of Standards and Technology (NIST) Ssulfate isotope reference materials (RM) in an attempt to correct for the difference. The ability of external isotope correction for Ssulfate isotope measurements was evaluated by analyzing NIST and United States Geological Survey (USGS) Ssulfate isotope reference materials as unknowns. Differences in δ34Ssulfate between standard-sample bracketing and standard-sample bracketing with external isotope correction for sulfate samples ranged from 0.72‰ to 2.35‰ over a δ34S range of 1.40‰ to 21.17‰. No isotopic differences were observed when analyzing Ssulfide reference materials over a δ34Ssulfide range of − 32.1‰ to 17.3‰ and a δ33S range of − 16.5‰ to 8.9‰ via laser ablation (LA)-MC-ICP-MS. Here, we identify a possible plasma induced fractionation for Ssulfate and describe a new method using external isotope calibration corrections using solution and LA-MC-ICP-MS.

Matrix Effects Originating from Coexisting Minerals and Accurate Determination of Stable Silver Isotopes in Silver Deposits.

PubMed

Guo, Qi; Wei, Hai-Zhen; Jiang, Shao-Yong; Hohl, Simon; Lin, Yi-Bo; Wang, Yi-Jing; Li, Yin-Chuan

2017-12-19

Except for extensive studies in core formation and volatile-element depletion processes using radiogenic Ag isotopes (i.e., the Pd-Ag chronometer), recent research has revealed that the mass fractionation of silver isotopes is in principle controlled by physicochemical processes (e.g., evaporation, diffusion, chemical exchange, etc.) during magmatic emplacement and hydrothermal alteration. As these geologic processes only produce very minor variations of δ 109 Ag from -0.5 to +1.1‰, more accurate and precise measurements are required. In this work, a robust linear relationship between instrumental mass discrimination of Ag and Pd isotopes was obtained at the Ag/Pd molar ratio of 1:20. In Au-Ag ore deposits, silver minerals have complex paragenetic relationships with other minerals (e.g., chalcopyrite, sphalerite, galena, pyrite, etc.). It is difficult to remove such abundant impurities completely because the other metals are tens to thousands of times richer than silver. Both quantitative evaluation of matrix effects and modification of chemical chromatography were carried out to deal with the problems. Isobaric inferences (e.g., 65 Cu 40 Ar + to 105 Pd, 208 Pb 2+ to 104 Pd, and 67 Zn 40 Ar + to 107 Ag + ) and space charge effects dramatically shift the measured δ 109 Ag values. The selection of alternative Pd isotope pairs is effective in eliminating spectral matrix effects so as to ensure accurate analysis under the largest possible ranges for metal impurities, which are Cu/Ag ≤ 50:1, Fe/Ag ≤ 600:1, Pb/Ag ≤ 10:1, and Zn/Ag ≤ 1:1, respectively. With the modified procedure, we reported silver isotope compositions (δ 109 Ag) in geological standard materials and typical Au-Ag ore deposit samples varying from -0.029 to +0.689 ‰ with external reproducibility of ±0.009-0.084 ‰. A systemic survey of δ 109 Ag (or ε 109 Ag) variations in rocks, ore deposits, and environmental materials in nature is discussed.

Pb-Sr-Nd isotopes in surficial materials at the Pebble Porphyry Cu-Au-Mo Deposit, Southwestern Alaska: can the mineralizing fingerprint be detected through cover?

USGS Publications Warehouse

Ayuso, Robert A.; Kelley, Karen D.; Eppinger, Robert G.; Forni, Francesca

2013-01-01

The Cretaceous Pebble porphyry Cu-Au-Mo deposit is covered by tundra and glacigenic sediments. Pb-Sr-Nd measurements were done on sediments and soils to establish baseline conditions prior to the onset of mining operations and contribute to the development of exploration methods for concealed base metal deposits of this type. Pebble rocks have a moderate range for 206Pb/204Pb = 18.574 to 18.874, 207Pb/204Pb = 15.484 to 15.526, and 208,Pb/204Pb = 38.053 to 38.266. Mineralized granodiorite shows a modest spread in 87Sr/86Sr (0.704354–0.707621) and 143Nd/144Nd (0.512639–0.512750). Age-corrected (89 Ma) values for the granodiorite yield relatively unradiogenic Pb (e.g., 207Pb/204Pb 87Sr/86Sr, and positive values of ɛNd (1.00–4.52) that attest to a major contribution of mantle-derived source rocks. Pond sediments and soils have similar Pb isotope signatures and 87Sr/86Sr and 143Nd/144Nd values that resemble the mineralized granodiorites. Glacial events have obscured the recognition of isotope signatures of mineralized rocks in the sediments and soils. Baseline radiogenic isotope compositions, prior to the onset of mining operations, reflect natural erosion, transport and deposition of heterogeneous till sheets that included debris from barren rocks, mineralized granodiorite and sulfides from the Pebble deposit, and other country rocks that pre- and postdate the mineralization events. Isotopic variations suggest that natural weathering of the deposit is generally reflected in these surficial materials. The isotope data provide geochemical constraints to glimpse through the extensive cover and together with other geochemical observations provide a vector to concealed mineralized rocks genetically linked with the Pebble deposit.

New Production Routes for Medical Isotopes 64Cu and 67Cu Using Accelerator Neutrons

NASA Astrophysics Data System (ADS)

Kin, Tadahiro; Nagai, Yasuki; Iwamoto, Nobuyuki; Minato, Futoshi; Iwamoto, Osamu; Hatsukawa, Yuichi; Segawa, Mariko; Harada, Hideo; Konno, Chikara; Ochiai, Kentaro; Takakura, Kosuke

2013-03-01

We have measured the activation cross sections producing 64Cu and 67Cu, promising medical radioisotopes for molecular imaging and radioimmunotherapy, by bombarding a natural zinc sample with 14 MeV neutrons. We estimated the production yields of 64Cu and 67Cu by fast neutrons from \\text{natC(d,n) with 40 MeV 5 mA deuterons. We used the present result together with the evaluated cross section of Zn isotopes. The calculated 64Cu yield is 1.8 TBq (175 g 64Zn) for 12 h of irradiation; the yields of 67Cu by 67Zn(n,p)67Cu and 68Zn(n,x)67Cu were 249 GBq (184 g 67Zn) and 287 GBq (186 g 68Zn) at the end of 2 days of irradiation, respectively. From the results, we proposed a new route to produce 67Cu with very little radionuclide impurity via the 68Zn(n,x)67Cu reaction, and showed the 64Zn(n,p)64Cu reaction to be a promising route to produce 64Cu. Both 67Cu and 64Cu are noted to be produced using fast neutrons.

Application of non-traditional stable isotopes in analytical ecogeochemistry assessed by MC ICP-MS--A critical review.

PubMed

Irrgeher, Johanna; Prohaska, Thomas

2016-01-01

Analytical ecogeochemistry is an evolving scientific field dedicated to the development of analytical methods and tools and their application to ecological questions. Traditional stable isotopic systems have been widely explored and have undergone continuous development during the last century. The variations of the isotopic composition of light elements (H, O, N, C, and S) have provided the foundation of stable isotope analysis followed by the analysis of traditional geochemical isotope tracers (e.g., Pb, Sr, Nd, Hf). Questions in a considerable diversity of scientific fields have been addressed, many of which can be assigned to the field of ecogeochemistry. Over the past 15 years, other stable isotopes (e.g., Li, Zn, Cu, Cl) have emerged gradually as novel tools for the investigation of scientific topics that arise in ecosystem research and have enabled novel discoveries and explorations. These systems are often referred to as non-traditional isotopes. The small isotopic differences of interest that are increasingly being addressed for a growing number of isotopic systems represent a challenge to the analytical scientist and push the limits of today's instruments constantly. This underlines the importance of a metrologically sound concept of analytical protocols and procedures and a solid foundation of data processing strategies and uncertainty considerations before these small isotopic variations can be interpreted in the context of applied ecosystem research. This review focuses on the development of isotope research in ecogeochemistry, the requirements for successful detection of small isotopic shifts, and highlights the most recent and innovative applications in the field.

Petrogenesis of the mineralized granitoids from the Kounrad and Borly porphyry Cu deposits and the East Kounrad porphyry Mo deposit in Kazakhstan: Implication for tectonic evolution and mineralization of the western part of the Central Asian Orogenic Belt

NASA Astrophysics Data System (ADS)

Shen, Ping; Pan, Hongdi; Seitmuratova, Eleonora

2017-08-01

The Kounrad region, located in the western part of the Central Asian Orogenic Belt, hosts the Kounrad porphyry Cu, the Borly porphyry Cu-Mo, and the East Kounrad porphyry Mo deposits. Secondary ion mass spectrometry (SIMS) zircon U-Pb dating indicates that the mineralized granitoids from the Kounrad, the Borly and the East Kounrad deposits emplaced at 331.7 ± 2.2 Ma, 311.6 ± 2.6 Ma, and 295.4 ± 2.9 Ma, respectively. The mineralized granodiorite porphyries at Kounrad show a geochemical affinity to adakitic rocks with high Sr (357-670 ppm), Sr/Y (40-68) and Mg numbers (Mg# = molar Mg/(Mg + Fe2 +)) from 0.43 to 0.51, low Yb (0.97-1.1 ppm) and Y (8.3-11.1 ppm). They have variable Sr-Nd-Hf-O isotopic compositions ((87Sr/86Sr)i = 0.7046 to 0.7051, εNd(t) = - 0.1 to + 1.1, εHf(t) = + 5.2 to + 9.0, δ18O = + 5.7 to + 6.8). These features indicate that the Kounrad adakitic magmas derived from the MASH (melting, assimilation, storage, homogenization) zone at depth of 40 km with 5-15% ancient basement rocks contamination. The mineralized granodiorite porphyries at Borly have a normal arc magma geochemical signature (e.g., enrichment of light rare earth elements (LREE) and depletion of heavy REE, Nb and Ti) and experienced fractional crystallization. They also have variable Sr-Nd-Hf-O isotopic compositions ((87Sr/86Sr)i = 0.7047 to 0.7053, εNd(t) = 0 to - 1.3, εHf(t) = - 0.6 to + 7.4, δ18O = + 5.5 to + 6.7) and Mg# (0.45 to 0.51), indicating that they were generated by melting of juvenile basaltic lower crust with normal thickness, followed by 10-30% ancient crustal contamination. The East Kounrad mineralized intrusions, consisting of granite and leucogranite, have experienced advanced degrees of fractional crystallization and have similar Sr-Nd-Hf-O isotopic compositions ((87Sr/86Sr)i = 0.7048, ɛNd (t) = + 1.0 to + 2.8, εHf(t) = + 4.8 to + 8.9, δ18O = + 5.6 to + 6.4) and low Mg# (0.18-0.37), indicating a juvenile lower crust source at depths of < 27 km with 10-20% ancient crustal contamination. The link between geochemistry and mineralization indicate that the subduction of the Junggar-Balkhash Ocean at 332 Ma resulted in the formation of the Kounrad adakitic rocks and assocatied Cu deposit, and continuing subduction at around 311 Ma resulted in the formation of the Borly granodiorite porphyry and assocatied Cu-Mo deposit, but entered a collisional stage by the Early-Permian ( 295 Ma) and resulted in the formation of the East Kounrad granite and leucogranite and assocatied Mo deposit. It is likely that evolution from porphyry Cu to Mo mineralization in the Kounrad region is owing to tectonic evolution from subduction to collision settings, crust depth variation from thickness to thinness, and magma evolution from adaktic and normal arc magma to highly fractionated I-type granitic magma.

Compilation of minimum and maximum isotope ratios of selected elements in naturally occurring terrestrial materials and reagents

USGS Publications Warehouse

Coplen, T.B.; Hopple, J.A.; Böhlke, J.K.; Peiser, H.S.; Rieder, S.E.; Krouse, H.R.; Rosman, K.J.R.; Ding, T.; Vocke, R.D.; Revesz, K.M.; Lamberty, A.; Taylor, P.; De Bievre, P.

2002-01-01

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope abundance variations potentially are large enough to result in future expansion of their atomic weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope-abundance variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio. There are no internationally distributed isotopic reference materials for the elements zinc, selenium, molybdenum, palladium, and tellurium. Preparation of such materials will help to make isotope ratio measurements among laboratories comparable. The minimum and maximum concentrations of a selected isotope in naturally occurring terrestrial materials for selected chemical elements reviewed in this report are given below: Isotope Minimum mole fraction Maximum mole fraction -------------------------------------------------------------------------------- 2H 0 .000 0255 0 .000 1838 7Li 0 .9227 0 .9278 11B 0 .7961 0 .8107 13C 0 .009 629 0 .011 466 15N 0 .003 462 0 .004 210 18O 0 .001 875 0 .002 218 26Mg 0 .1099 0 .1103 30Si 0 .030 816 0 .031 023 34S 0 .0398 0 .0473 37Cl 0 .240 77 0 .243 56 44Ca 0 .020 82 0 .020 92 53Cr 0 .095 01 0 .095 53 56Fe 0 .917 42 0 .917 60 65Cu 0 .3066 0 .3102 205Tl 0 .704 72 0 .705 06 The numerical values above have uncertainties that depend upon the uncertainties of the determinations of the absolute isotope-abundance variations of reference materials of the elements. Because reference materials used for absolute isotope-abundance measurements have not been included in relative isotope abundance investigations of zinc, selenium, molybdenum, palladium, and tellurium, ranges in isotopic composition are not listed for these elements, although such ranges may be measurable with state-of-the-art mass spectrometry. This report is available at the url: http://pubs.water.usgs.gov/wri014222.

Origin and fate of sulfide liquids in hotspot volcanism (La Réunion): Pb isotope constraints from residual Fe-Cu oxides

NASA Astrophysics Data System (ADS)

Vlastélic, I.; Gannoun, A.; Di Muro, A.; Gurioli, L.; Bachèlery, P.; Henot, J. M.

2016-12-01

Immiscible sulfide liquids in basaltic magmas play an important role in trace metal transport and the sulfur budget of volcanic eruptions. However, sulfides are transient phases, whose origin and fate are poorly constrained. We address these issues by analyzing sulfide destabilization products preserved in lavas from La Réunion Island. Iron oxide globules and coatings, typically 20-80 μm in size, were found to occur in vesicles of differentiated lavas from Piton des Neiges, and recent pumice samples from Piton de la Fournaise. Field and mineralogical evidence indicates that the iron oxides are syn-eruptive phases not resulting from hydrothermal processes. Samples were first studied by Scanning Electron Microscopy. The globules were separated, whereas the smaller spherules and coatings were concentrated by magnetic sorting and acid leaching, and samples were processed through wet chemistry. The Fe oxide phases comprise 49-74 wt.% Fe, 26-40 wt.% O, and up to 6 wt.% Cu, 811 ppm Ni, 140 ppm Bi, and 8.5 ppm Pb. Compared to the host lava, Cu, Ni, and Bi are enriched by a factor of 101-103. Systematic Pb isotope disequilibrium (between 500 ppm and 2.9% for 206Pb/204Pb) exists between Fe oxides and host rocks, with Fe oxides generally displaying less radiogenic ratios. Unradiogenic Pb is a typical signature of sulfide, which tends to concentrate Pb, but not its parent elements U and Th. Thus, both the chemical and isotopic compositions of the vesicle-hosted Fe oxides suggest that they are more or less direct products of the destabilization of immiscible sulfide liquids. Although Pb dominantly partitions into the gas phase during sulfide breakdown, the original Pb isotope signature of sulfide is preserved in the residual oxide. The composition estimated for the parent sulfides (206Pb/204Pb = 18.20-18.77, 207Pb/204Pb = 15.575, and 208Pb/204Pb = 38.2-38.8) precludes a genetic link with the La Réunion plume, and suggests a lithospheric or crustal origin. It is estimated that magma ascent velocities at Piton de la Fournaise are high enough to counterbalance the settling velocities of millimeter-size sulfides. Despite their high density, sulfide liquids are thus transferred upward during eruptions and their destabilization contributes to SO2 emanations. Assimilation of foreign sulfides from the lithosphere can explain why SO2 emissions sometimes (e.g., during the April 2007 eruption) exceed those predicted from the S content of melt inclusions.

Petrogenesis of Ore-Bearing and Ore-Barren Intermediate-Acid Intrusive Rocks from Jilongshan Au-Cu Skarn Deposit , the Middle-Lower Yangtze River Metallogenic Belt, Eastern China and their Geological Implications

NASA Astrophysics Data System (ADS)

Zhan, X.; Wei, J.; Chen, M.; Zhao, X.

2017-12-01

Jilongshan Au-Cu skarn deposit in Edong-Jiurui ore district , Middle-Lower Yangtze River Metallogenic Belt(MLYRB) , eastern China ,contains 44 t gold and 32 Mt of copper ores. The mineralization is dominated by massive skarn ores, most of which occurs along the contact zone between the lower Triassic dolomitic limestones and Jilongshan granodioritic intrusion. However, Baiguoshu pluton, no more than 1 km western, has been not found any mineralized occurrence with the same strata. The ore-bearing and ore-barren intrusive rocks are granodiorite porphyries, could not be identified by petrographic characters. Besides, Zircon U-Pb dating results demonstrate that Jilongshan and Baiguoshu intrusion emplaced at 140 ± 1Ma and 141 ± 1 Ma respectively, coeval with the Early Cretaceous magmatism in Edong-Jiurui area. Elements geochemistry present that they are both characterized by high Al2O3, rich Na2O (Na2O/K2O>1.0), enrichment of LILE (Rb, Ba, K, Sr) and depletion of HFSE (Nb, Ta), and weak negative Eu anomalies, which suggest they may be originated from partial melting of enriched mantle and associated with crust-mantle interaction ,evidenced by the Sr-Nd-Hf isotopic composition as well. Although the two are partly geochemically similar with each other, they have some obvious differences. The former have higher K2O and Y, Yb ,lower MgO, and Cr, Ni contents, and more obvious differentiation degree between light and heavy REEs with (La/Yb)N=10.55-15.95 than the latter with (La/Yb)N=8.67-10.47. It is indicated that the magmas of the Jilongshan intrusive rocks were probably derived from deeper source than that of the Baiguoshu, also supported by mineralogical data of biotite. In addition, Jilongshan intrusive rocks have a relatively higher initial Nd (ɛNd (t) = -8.2 - -9.4) and Sr ((87Sr/86Sr)i=0.70822-0.70897) isotopic composition than Baiguoshu (-9.2 - -9.7 and 0.70855-0.70881), as same as Lu-Hf isotopic composition. Therefore, combined with previous studies, we suggest that the Jilongshan granodiorite porphyry originated as partial melts of an enriched mantle source experienced more sufficient interaction with lower crust materials during magma ascent compared with Baiguoshu granodiorite porphyry, which may lead to Cu-Au enriched magmas, contributing to subsequent mineralization.

Selected isotope ratio measurements of light metallic elements (Li, Mg, Ca, and Cu) by multiple collector ICP-MS

PubMed Central

Platzner, Thomas I.; Segal, Irina

2007-01-01

The unique capabilities of multiple collector inductively coupled mass spectrometry (MC-ICP-MS) for high precision isotope ratio measurements in light elements as Li, Mg, Ca, and Cu are reviewed in this paper. These elements have been intensively studied at the Geological Survey of Israel (GSI) and other laboratories over the past few years, and the methods used to obtain high precision isotope analyses are discussed in detail. The scientific study of isotopic fractionation of these elements is significant for achieving a better understanding of geochemical and biochemical processes in nature and the environment. PMID:17962922

Cu, Fe, and Zn Isotope Variations Within a High-Temperature Mid-Ocean Ridge Sulfide Structure

NASA Astrophysics Data System (ADS)

Ewing, S. M.; Nelson, B. K.; Kelley, D. S.; Nielsen, D. C.

2006-12-01

Hydrothermal processes at mid-ocean ridges play an important role in controlling the transition metal budget of seawater and the crust through which it circulates. Preliminary work has shown stable metal isotope variations accompany these processes. We report Cu, Zn, and Fe isotope analyses of transects through a high temperature sulfide structure ("Fin") collected during the 1998 Edifice Rex Sulfide Recovery Project. We analyzed two horizontal transects through the sulfide edifice, from inner conduit to outer surface. Transects A and F are 9 and 6 cm in length, respectively. Each displays radially zoned mineralogy progressing from a chalcopyrite (ccp) zone through zones of zinc sulfide, pyrite-anhydrite (pyr-anh) matrix, zinc sulfide-anhydrite (zns-anh) matrix, to an outer well-cemented silica (Si) zone. Additional ccp and pyr-anh zones appear in transect A resulting from a smaller breakout conduit. In transect A, Cu displays the most isotopic variation, with little variation in Fe and Zn isotopes. From the inner ccp zone outward, the Cu isotope profile shows a 0.4‰ (±0.05‰ 2σ) increase in the first pyr-anh zone over the coarse-grained ccp zone. The δ65Cu drops by 0.6‰ in the secondary ccp zone and recovers to values of the innermost wall in the following zone where it is constant until the outermost portion of the Si rich zone, which shows a 1.3‰ increase over inner zone values. The Zn isotope profile has a total variation of 0.27‰ (±0.05‰ 2σ), with a 0.2‰ increase in the first pyr- anh zone followed by a .27‰ decrease in the adjacent zone, and recovering to its heaviest values in the second pyr-anh zone. The Zn profile lacks any significant increase of the δ^{64}Zn in the outermost zones. The Fe isotope profile shows very little variation across the chimney wall, but does have a sharp 0.7‰ (±0.1‰ 2σ) increase in the δ56Fe in the well-cemented Si rich zone. In transect F, the Cu isotope profile again shows the most variation, but displays a more pronounced jump of 1.3‰ at the zinc sulfide boundary and no obvious increase of the δ65Cu in the Si rich zone. Similarly with Zn, there is a 0.35‰ increase of the δ^{64}Zn, but no outer wall increase. Fe, on the other hand, has variation of the same order as transect A, and shows a 0.6‰ increase of the δ56Fe in both the zns-anh and Si rich zones. These profiles are likely the result of a combination of diffusion and advection processes, fluid mineral equilibria, and mineral-mineral equilibria. High δ values of the outer zones likely reflect oxidation reactions with seawater. Processes responsible for isotopic variations within interior zones of the structure are ambiguous. Kinetic effects and biological activity may play a role, as Zn, which is not redox sensitive and only minimally coordination sensitive, has profiles that are qualitatively similar to Cu and Fe, but less analytically pronounced. Our findings are within the range of other published results, and further illustrate such measurable metal isotope variation exists not only on the vent field scale among chimneys, but systematically within chimney walls.

Capture of heavy hydrogen isotopes in a metal-organic framework with active Cu(I) sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weinrauch, Ingrid; Savchenko, Ievgeniia L.; Denysenko, D.

The production of pure deuterium and the removal of tritium from nuclear waste are the key challenges in separation of light isotopes. Presently, the technological methods are extremely energy- and cost-intensive. Here we report the capture of heavy hydrogen isotopes from hydrogen gas by selective adsorption at Cu(I) sites in a metal-organic framework. At the strongly binding Cu(I) sites (32 kJ mol -1) nuclear quantum effects result in higher adsorption enthalpies of heavier isotopes. The capture mechanism takes place most efficiently at temperatures above 80 K, when an isotope exchange allows the preferential adsorption of heavy isotopologues from the gasmore » phase. Large difference in adsorption enthalpy of 2.5 kJ mol -1 between D 2 and H 2 results in D 2-over-H 2 selectivity of 11 at 100 K, to the best of our knowledge the largest value known to date. Combination of thermal desorption spectroscopy, Raman measurements, inelastic neutron scattering and first principles calculations for H 2/D 2 mixtures allows the prediction of selectivities for tritium-containing isotopologues.« less

Capture of heavy hydrogen isotopes in a metal-organic framework with active Cu(I) sites

DOE PAGES

Weinrauch, Ingrid; Savchenko, Ievgeniia L.; Denysenko, D.; ...

2017-03-06

The production of pure deuterium and the removal of tritium from nuclear waste are the key challenges in separation of light isotopes. Presently, the technological methods are extremely energy- and cost-intensive. Here we report the capture of heavy hydrogen isotopes from hydrogen gas by selective adsorption at Cu(I) sites in a metal-organic framework. At the strongly binding Cu(I) sites (32 kJ mol -1) nuclear quantum effects result in higher adsorption enthalpies of heavier isotopes. The capture mechanism takes place most efficiently at temperatures above 80 K, when an isotope exchange allows the preferential adsorption of heavy isotopologues from the gasmore » phase. Large difference in adsorption enthalpy of 2.5 kJ mol -1 between D 2 and H 2 results in D 2-over-H 2 selectivity of 11 at 100 K, to the best of our knowledge the largest value known to date. Combination of thermal desorption spectroscopy, Raman measurements, inelastic neutron scattering and first principles calculations for H 2/D 2 mixtures allows the prediction of selectivities for tritium-containing isotopologues.« less

Microstructure and Thermal Conductivity of Carbon Nanotube Reinforced Cu Composites.

PubMed

Chen, Pingan; Zhang, Jian; Shen, Qiang; Luo, Guoqiang; Dai, Yang; Wang, Chuanbing; Li, Meijuan; Zhang, Lianmeng

2017-04-01

Microstructure and thermal conductivity (TC) of carbon nanotubes reinforced Cu (CNT-Cu) composites have been studied. When CNTs were coated with nano Cu by electroless plating, the TC of CNT-Cu composites showed a noticeable improvement and increased with CNT contents. When 1.0 vol% CNTs was added, the TC of CNT-Cu composites increased to 420.4 W/(m · K), 30% higher than that of monolithic Cu (323.1 W/(m · K)). According to the measured TC of CNT-Cu composites, the interfacial thermal resistance of CNT-Cu composites was calculated as 3.0 × 10⁻⁹ m² K/W which was lower than the reported values of CNTs reinforced polymer matrix composites and ceramic matrix composites. Microstructures showed that CNTs modified with nano Cu were homogeneously dispersed and embedded in the Cu matrix, indicating that there was strong bonding between CNTs and Cu. The homogeneously dispersed CNTs and reduction of interfacial thermal resistance resulted in the improvement of thermal conductivity of CNT-Cu composites. Therefore, the prepared CNT-Cu composites are promising materials for thermal management applications.

Isotopic variability of cave bears (δ15N, δ13C) across Europe during MIS 3

NASA Astrophysics Data System (ADS)

Krajcarz, Magdalena; Pacher, Martina; Krajcarz, Maciej T.; Laughlan, Lana; Rabeder, Gernot; Sabol, Martin; Wojtal, Piotr; Bocherens, Hervé

2016-01-01

Collagen, the organic fraction of bone, records the isotopic parameters of consumed food for carbon (δ13C) and nitrogen (δ15N). This relationship of isotopic signature between diet and tissue is an important tool for the study of dietary preferences of modern and fossil animal species. Since the first information on the isotopic signature of cave bear was reported, numerous data from Europe have become available. The goal of this work is to track the geographical variation of cave bear collagen isotopic values in Europe during Marine Isotopic Stage 3 (about 60,000-25,000 yr BP). In this study the results of new δ13C and δ15N isotopic analyses of cave bear collagen from four Central-Eastern European sites are presented, as well as a review of all published isotopic data for cave bears of the same period. The main conclusion is a lack of geographical East-West pattern in the variations of δ13C and δ15N values of cave bear collagen. Moreover, no relationship was found between cave bear taxonomy and isotopic composition. The cave bears from Central-Eastern Europe exhibit δ13C and δ15N values near the average of the range of Central, Western and Southern European cave bears. Despite the fact that most cave bear sites follow an altitudinal gradient, separate groups of sites exhibit shift in absolute values of δ13C, what disturbs an altitude-related isotopic pattern. The most distinct groups are: high Alpine sites situated over 1500 m a.s.l. - in terms of δ13C; and two Romanian sites Peştera cu Oase and Urşilor - in case of δ15N. Although the cave bear isotopic signature is driven by altitude, the altitudinal adjustment of isotopic data is not enough to explain the isotopic dissimilarity of these cave bears. The unusually high δ15N signature of mentioned Romanian sites is an isolated case in Europe. Cave bears from relatively closely situated Central-Eastern European sites and other Romanian sites are more similar to Western European than to Romanian populations in terms of isotopic composition, and probably ecology.

The isotopic composition of cosmic-ray beryllium and its implication for the cosmic ray's age

NASA Technical Reports Server (NTRS)

Lukasiak, A.; Ferrando, P.; Mcdonald, F. B.; Webber, W. R.

1994-01-01

We report a new measurement of the cosmic-ray isotopic composition of beryllium in the low-energy range from 35 to 113 MeV per nucleon. This measurement was made using the High Energy Telescope of the CRS experiment on the Voyager 1 and 2 spacecraft during the time period from 1977 to 1991. In this overall time period of 14 years the average solar modulation level was about 500 MV. The cosmic-ray beryllium isotopes were completely separated with an average mass resolution sigma of 0.185 amu. The isotope fractions of Be-7, Be-9, and Be-10 obtained are 52.4 +/- 2.9%, 43.3 +/- 3.7%, and 4.3 +/- 1.5%, respectively. The measured cosmic-ray abundances of Be-7 and Be-9 are found to be in agreement with calculations based on standard Leaky-Box model for the interstellar propagation of cosmic-ray nuclei using the recent cross sections of the New Mexico-Saclay collaboration. From our observed ratio Be-10/Be = 4.3 +/- 1.5% we deduce an average interstellar density of about 0.28 (+0.14, -0.11) atoms/cu cm, and acosmic-ray lifetime for escape of 27 (+19, -9) x 10(exp 6) years. The surviving fraction of Be-10 is found to be 0.19 +/- 0.07. Modifications to the conclusions of the Leaky-Box model when a diffusion + convection halo model for propagation is used are also considered.

The isotopic composition of cosmic-ray beryllium and its implication for the cosmic ray's age

NASA Astrophysics Data System (ADS)

Lukasiak, A.; Ferrando, P.; McDonald, F. B.; Webber, W. R.

1994-03-01

We report a new measurement of the cosmic-ray isotopic composition of beryllium in the low-energy range from 35 to 113 MeV per nucleon. This measurement was made using the High Energy Telescope of the CRS experiment on the Voyager 1 and 2 spacecraft during the time period from 1977 to 1991. In this overall time period of 14 years the average solar modulation level was about 500 MV. The cosmic-ray beryllium isotopes were completely separated with an average mass resolution sigma of 0.185 amu. The isotope fractions of Be-7, Be-9, and Be-10 obtained are 52.4 +/- 2.9%, 43.3 +/- 3.7%, and 4.3 +/- 1.5%, respectively. The measured cosmic-ray abundances of Be-7 and Be-9 are found to be in agreement with calculations based on standard Leaky-Box model for the interstellar propagation of cosmic-ray nuclei using the recent cross sections of the New Mexico-Saclay collaboration. From our observed ratio Be-10/Be = 4.3 +/- 1.5% we deduce an average interstellar density of about 0.28 (+0.14, -0.11) atoms/cu cm, and a cosmic-ray lifetime for escape of 27 (+19, -9) x 106 years. The surviving fraction of Be-10 is found to be 0.19 +/- 0.07. Modifications to the conclusions of the Leaky-Box model when a diffusion + convection halo model for propagation is used are also considered.

Electroless Plated Nanodiamond Coating for Stainless Steel Passivation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, D.; Korinko, P.; Spencer, W.

Tritium gas sample bottles and manifold components require passivation surface treatments to minimize the interaction of the hydrogen isotopes with surface contamination on the stainless steel containment materials. This document summarizes the effort to evaluate electroless plated nanodiamond coatings as a passivation layer for stainless steel. In this work, we developed an electroless nanodiamond (ND)-copper (Cu) coating process to deposit ND on stainless steel parts with the diamond loadings of 0%, 25% and 50% v/v in a Cu matrix. The coated Conflat Flanged Vessel Assemblies (CFVAs) were evaluated on surface morphology, composition, ND distribution, residual hydrogen release, and surface reactivitymore » with deuterium. For as-received Cu and ND-Cu coated CFVAs, hydrogen off-gassing is rapid, and the off-gas rates of H 2 was one to two orders of magnitude higher than that for both untreated and electropolished stainless steel CFVAs, and hydrogen and deuterium reacted to form HD as well. These results indicated that residual H 2 was entrapped in the Cu and ND-Cu coated CFVAs during the coating process, and moisture was adsorbed on the surface, and ND and/or Cu might facilitate catalytic isotope exchange reaction for HD formation. However, hydrocarbons (i.e., CH 3) did not form, and did not appear to be an issue for the Cu and ND-Cu coated CFVAs. After vacuum heating, residual H 2 and adsorbed H 2O in the Cu and ND-Cu coated CFVAs were dramatically reduced. The H 2 off-gassing rate after the vacuum treatment of Cu and 50% ND-Cu coated CFVAs was on the level of 10 -14 l mbar/s cm 2, while H 2O off-gas rate was on the level of 10 -15 l mbar/s cm 2, consistent with the untreated or electropolished stainless steel CFVA, but the HD formation remained. The Restek EP bottle was used as a reference for this work. The Restek Electro-Polished (EP) bottle and their SilTek coated bottles tested under a different research project exhibited very little hydrogen off-gassing and unmeasurable HD formation. ND and Cu were initially chosen to develop improved passivation technology, because Cu has a lower permeability of hydrogen, and diamond is more inert than other materials under a hydrogen atmosphere. However, our tests demonstrated that even after an 8-18 day vacuum extraction heat treatment, the electroless plated Cu and ND-Cu coated stainless steel CFVAs exhibited H 2 off-gassing rates that were just comparable to those for the untreated or electropolished stainless steel CFVA, and the HD formation was still observed. Thus, the Restek Electro-Polished (EP) bottle outperformed the electroless plated Cu and ND-Cu coated stainless steel CFVAs, and the electroless plated nanodiamond coating is not promising as a surface passivation technology. However, the ND-Cu coating may be beneficial to another application in which catalyzing the H 2-D 2 exchange reaction is desired.« less

Sulfide enrichment at an oceanic crust-mantle transition zone: Kane Megamullion (23°N, MAR)

NASA Astrophysics Data System (ADS)

Ciazela, Jakub; Koepke, Juergen; Dick, Henry J. B.; Botcharnikov, Roman; Muszynski, Andrzej; Lazarov, Marina; Schuth, Stephan; Pieterek, Bartosz; Kuhn, Thomas

2018-06-01

The Kane Megamullion oceanic core complex located along the Mid-Atlantic Ridge (23°30‧N, 45°20‧W) exposes lower crust and upper mantle directly on the ocean floor. We studied chalcophile elements and sulfides in the ultramafic and mafic rocks of the crust-mantle transition and the mantle underneath. We determined mineralogical and elemental composition and the Cu isotope composition of the respective sulfides along with the mineralogical and elemental composition of the respective serpentines. The rocks of the crust-mantle transition zone (i.e., plagioclase harzburgite, peridotite-gabbro contacts, and dunite) overlaid by troctolites are by one order of magnitude enriched in several chalcophile elements with respect to the spinel harzburgites of the mantle beneath. Whereas the range of Cu concentrations in spinel harzburgites is 7-69 ppm, the Cu concentrations are highly elevated in plagioclase harzburgites with a range of 90-209 ppm. The zones of the peridotite-gabbro contacts are even more enriched, exhibiting up to 305 ppm Cu and highly elevated concentrations of As, Zn, Ga, Sb and Tl. High Cu concentrations show pronounced correlation with bulk S concentrations at the crust-mantle transition zone implying an enrichment process in this horizon of the oceanic lithosphere. We interpret this enrichment as related to melt-mantle reaction, which is extensive in crust-mantle transition zones. In spite of the ubiquitous serpentinization of primary rocks, we found magmatic chalcopyrites [CuFeS2] as inclusions in plagioclase as well as associated with pentlandite [(Fe,Ni)9S8] and pyrrhotite [Fe1-xS] in polysulfide grains. These chalcopyrites show a primary magmatic δ65Cu signature ranging from -0.04 to +0.29 ‰. Other chalcopyrites have been dissolved during serpentinization. Due to the low temperature (<300 °C) of circulating fluids chalcophile metals from primary sulfides have not been mobilized and transported away but have been trapped in smaller secondary sulfides and hydroxides. Combined with the Cu deposits documented in the crust-mantle transition zones of various ophiolite complexes, our results indicate that the metal enrichment, increased sulfide modes, and potentially formation of small sulfide deposits could be expected globally along the petrological Moho.

Isotope effect in acetylene C2H2 and C2D2 rotations on Cu(001)

NASA Astrophysics Data System (ADS)

Shchadilova, Yulia E.; Tikhodeev, Sergei G.; Paulsson, Magnus; Ueba, Hiromu

2014-04-01

A comprehensive analysis of the elementary processes behind the scanning tunneling microscope controlled rotation of C2H2 and C2D2, isotopologues of a single acetylene molecule adsorbed on the Cu(001) surface, is given, with a focus on the isotope effects. With the help of density-functional theory we calculate the vibrational modes of C2H2 and C2D2 on Cu(001) and estimate the anharmonic couplings between them, using a simple strings-on-rods model. The probability of the elementary processes, nonlinear and combination band, is estimated using the Keldysh diagram technique. This allows us to clarify the main peculiarities and the isotope effects of the C2H2 and C2D2 on Cu(001) rotation, discovered in the pioneering work [B. C. Stipe et al., Phys. Rev. Lett. 81, 1263 (1998), 10.1103/PhysRevLett.81.1263], which have not been previously understood.

Mesozoic magmatism and timing of epigenetic Pb-Zn-Ag mineralization in the western Fortymile mining district, east-central Alaska: Zircon U-Pb geochronology, whole-rock geochemistry, and Pb isotopes

USGS Publications Warehouse

Dusel-Bacon, Cynthia; Aleinkoff, J.N.; Day, W.C.; Mortensen, J.K.

2015-01-01

Epigenetic Pb-Zn-Ag ± Cu prospects in the western Fortymile district are spatially associated with splays of the northeast-trending Kechumstuk sinistral-normal fault zone and with ca. 68-66 Ma felsic intrusions and dikes. The similarity between Pb isotope compositions of feldspars from the Late Cretaceous igneous bodies and sulfides from the epithermal prospects suggests a Late Cretaceous age for most of the mineralization. Fluid flow along the faults undoubtedly played a major role in mineralization. We interpret displacement on the northeast-trending faults to be a far-field effect of dextral translation along Late Cretaceous plate-scale boundaries and faults that were roughly parallel to the subsequently developed Denali and Tintina fault systems, which currently bound the region.

Metal distribution and mobility in lateritic soils affected by Cu-Co smelting in the Copperbelt district, Zambia

NASA Astrophysics Data System (ADS)

Ettler, Vojtech; Mihaljevic, Martin; Majer, Vladimir; Kribek, Bohdan; Sebek, Ondrej

2010-05-01

The copper smelting activities in the Copperbelt mining district (Zambia) left a huge pollution related to the disposal sites of smelting waste (slags) and to the continuous deposition of the smelter stack particulates in the soil systems. We sampled 196 surface and subsurface soils in the vicinity of the Nkana copper smelter at Kitwe and a 110 cm deep lateritic soil profile in order to assess the regional distribution of metallic contaminants and their vertical mobility. The content of contaminants in soil samples were measured by ICP techniques and the lead isotopic compositions (206Pb/207Pb and 208Pb/206Pb ratios) were determined by ICP-MS. The spatial distribution of the major contaminants (Cu, Co, Pb, Zn) indicated the highest contamination NW of the smelter stack corresponding to the direction of prevailing winds in the area. The highest metal concentrations in soils were: 27410 ppm Cu, 606 ppm Co, 480 ppm Pb, 450 ppm Zn. Lead isotopes helped to discriminate the extent of metallic pollution related to the smelter emissions having similar 206Pb/207Pb ratio of 1.17-1.20 in contrast to the regional background value of 1.32. The investigation of the lateritic soil profile sampled in the near vicinity of the Nkana smelter indicated that contamination is mostly located in the uppermost soil horizons enriched in organic matter (< 10 cm). The sequential extraction procedure indicated that up to 33% of Cu and <10% of Co, Pb and Zn was mobile in the profile, being bound in the exchangeable fraction. However, in the deeper parts of the soil profile, metals were mostly bound in reducible fraction, presumably to hydrous ferric oxides. The combination of sequential extraction and lead isotopic determination indicated that the "mobile" fractions of Pb in the soil profile corresponded to the signatures of smelter particulate emissions (206Pb/207Pb = 1.17-1.20), which means that the anthropogenic emissions are the important source of mobile (and potentially bioavailable) metals.

Extreme variation of sulfur isotopic compositions in pyrite from the Qiuling sediment-hosted gold deposit, West Qinling orogen, central China: An in situ SIMS study with implications for the source of sulfur

USGS Publications Warehouse

Chen, Lei; Li, Xian-hua; Li, Jian-wei; Hofstra, Albert H.; Liu, Yu; Koenig, Alan E.

2015-01-01

High spatial resolution textural (scanning electron microscope (SEM)), chemical (electron microprobe (EMP)) and laser ablation-inductively coupled plasma-mass spec- trometry (LA-ICP-MS)), and sulfur isotopic (secondary ion mass spectrometry (SIMS)) analyses of pyrite from the Qiuling sediment-hosted gold deposit (232±4 Ma) in the West Qinling orogen, central China were conducted to distinguish pyrite types and gain insights into the source and evolution of sulfur in hydrothermal fluids. The results reveal an enormous variation (−27.1 to +69.6‰) in sulfur isotopic composition of pyrite deposited during three paragenetic stages. Pre-ore framboidal pyrite, which is characterized by low concentra- tions of As, Au, Cu, Co, and Ni, has negative δ34S values of −27.1 to −7.6‰ that are interpreted in terms of bacterial re- duction of marine sulfate during sedimentation and diagenesis of the Paleozoic carbonate and clastic sequences, the predom- inant lithologies in the deposit area, and the most important hosts of many sediment-hosted gold deposits throughout the West Qinling orogen. The ore-stage hydrothermal pyrite con- tains high concentrations of Au, As, Cu, Sb, Tl, and Bi and hasa relatively narrow range of positive δ34S values ranging from +8.1 to +15.2‰. The sulfur isotope data are comparable to those of ore pyrite from many Triassic orogenic gold deposits and Paleozoic sedimentary exhalative (SEDEX) Pb-Zn de- posits in the West Qinling orogen, both being hosted mainly in the Devonian sequence. This similarity indicates that sulfur, responsible for the auriferous pyrite at Qiuling, was largely derived from the metamorphic devolatization of Paleozoic marine sedimentary rocks. Post-ore-stage pyrite, which is sig- nificantly enriched in Co and Ni but depleted in Au and As, has unusually high δ34S values ranging from +37.4 to +69.6 ‰, that are interpreted to result from thermochemical reduc- tion of evaporite sulfates in underlying Cambrian sedimentary rocks with very high δ34S values. The variations in Au content and sulfur isotopic compositions across a single ore-stage py- rite grain may reflect displacement of indigenous groundwater with low δ34S values by auriferous metamorphic fluids with high δ34S values. The very low-grade metamorphism of the host rocks and the metamorphic derivation of sulfur for the ore pyrite indicate that the Qiuling sediment-hosted gold deposit is an epizonal manifestation of an orogenic gold system in the West Qinling orogen.

Linking Barbados Mineral Dust Aerosols to North African Sources Using Elemental Composition and Radiogenic Sr, Nd, and Pb Isotope Signatures

NASA Astrophysics Data System (ADS)

Bozlaker, Ayse; Prospero, Joseph M.; Price, Jim; Chellam, Shankararaman

2018-01-01

Large quantities of African dust are carried across the Atlantic to the Caribbean Basin and southern United States where it plays an important role in the biogeochemistry of soils and waters and in air quality. Dusts' elemental and isotopic composition was comprehensively characterized in Barbados during the summers of 2013 and 2014, the season of maximum dust transport. Although total suspended insoluble particulate matter (TSIP) mass concentrations varied significantly daily and between the two summers, the abundances (μg element/g TSIP) of 50 elements during "high-dust days" (HDD) were similar. Aerosols were regularly enriched in Na, Cu, Zn, As, Se, Mo, Cd, Sn, Sb, and W relative to the upper continental crust. Enrichment of these elements, many of which are anthropogenically emitted, was significantly reduced during HDD, attributed to mixing and dilution with desert dust over source regions. Generally, Ti/Al, Si/Al, Ca/Al, Ti/Fe, Si/Fe, and Ca/Fe ratios during HDD differed from their respective values in hypothesized North African source regions. Nd isotope composition was relatively invariant for "low-dust days" (LDD) and HDD. In contrast, HDD-aerosols were more radiogenic exhibiting higher 87Sr/86Sr, 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios compared to LDD. Generally, Barbados aerosols' composition ranged within narrow limits and was much more homogeneous than that of hypothesized African source soils. Our results suggest that summertime Barbados aerosols are dominated by a mixture of particles originating from sources in the Sahara-Sahel regions. The Bodélé Depression, long suspected as a major source, appears to be an insignificant contributor of summertime western Atlantic dust.

Enrichment and geochemical mobility of heavy metals in bottom sediment of the Hoedong reservoir, Korea and their source apportionment.

PubMed

Lee, Pyeong-Koo; Kang, Min-Ju; Yu, Soonyoung; Ko, Kyung-Seok; Ha, Kyoochul; Shin, Seong-Cheon; Park, Jung Han

2017-10-01

Physicochemical characteristics of bottom sediment in the Hoedong reservoir were studied to evaluate the effectiveness of the reservoir as traps for trace metals. Roadside soil, stream sediment and background soil were also studied for comparison. Sequential extractions were carried out, and lead isotopic compositions of each extraction were determined to apportion Pb sources. Besides, particle size distribution of roadside soil, and metal concentrations and Pb isotopes of each size group were determined to characterize metal contamination. In result, Zn and Cu were enriched in sediment through roadside soil. The data on metal partitioning implied that Zn posed potential hazards for water quality. Meanwhile, the noticeable reduction of the 206 Pb/ 207 Pb isotopic ratio in the acid-soluble fraction in the size group 200 μm - 2 mm of national roadside soil indicated that this size group was highly contaminated by automotive emission with precipitation of acid-soluble secondary minerals during evaporation. Based on the Pb isotopic ratios, the dry deposition of Asian dust (AD) and non-Asian dust (NAD) affected roadside soil, while the effects of AD and NAD on bottom sediment appeared to be low given the low metal concentrations in sediment. Metal concentrations and Pb isotopic compositions indicated that sediments were a mixture of background and roadside soil. Source apportionment calculations showed that the average proportion of traffic Pb in bottom and stream sediments was respectively 34 and 31% in non-residual fractions, and 26 and 28% in residual fraction. The residual fraction of sediments appeared to be as contaminated as the non-residual fractions. Copyright © 2017 Elsevier Ltd. All rights reserved.

The Nature and Origin of the ~1.88 Ga Circum-Superior Large Igneous Province

NASA Astrophysics Data System (ADS)

Minifie, M.; Kerr, A. C.; Ernst, R. E.

2009-12-01

The Circum-Superior Large Igneous Province (LIP) is composed of a discontinuous belt of magmatic rocks, predominantly mafic-ultramafic in composition, circumscribing the cratonic margins of the Superior Province in the Canadian Shield for >3000 km. In addition to the cratonic margin magmatism, magmatic rocks of the same age are found in the interior of the craton in the form of mafic-ultramafic dykes and also carbonatite complexes along the Kapuskasing Structural Zone. Recent U-Pb geochronological studies have shown a tight age grouping for these magmatic rocks between 1885 and 1864 Ma. Previous studies have treated the various segments of the Circum-Superior LIP individually and models on the origin of the magmatism include seafloor spreading, back-arc basin rifting, foredeep basin flexure, volcanic arc activity, transtension in pull-apart basins, and mantle plume activity. This study is the first to create a cohesive geochemical and Sr-Nd-Pb-Hf-Os isotopic database for the whole of the Circum-Superior LIP and to assess its petrogenesis as a single entity. The geochemical and isotopic evidence strongly favour a mantle plume origin for the Circum-Superior LIP magmatism. A common trace element signature, very much like that of the Ontong Java oceanic plateau, is persistent throughout most of this LIP. Most samples possess Zr/Y and Nb/Y ratios almost identical to Ontong Java and other oceanic plateau lavas. Utilisation of the PRIMELT2 software of Herzberg & Asimow (2008) shows that the parental magmas of the Circum-Superior LIP were derived from ~30-35% pooled fractional melting of a source composition similar to that of primitive mantle with 1% continental crust extracted from it at mantle potential temperatures ranging from 1515 to 1610° C. Basalts from islands in Hudson Bay possess slightly enriched trace element profiles with small positive Nb anomalies and highlight a degree of heterogeneity within the plume source. The Circum-Superior LIP magmatic rocks possess similar isotopic compositions which further support the notion of a common mantle source for the whole LIP. The isotopic composition of this source is distinct to that of N-MORB which precludes the role of ambient upper mantle in the petrogenesis of the Circum-Superior magmatism suggested by previous studies. Ni-Cu-PGE sulphide deposits are associated with some regions of the Circum-Superior LIP. Subtle differences in the geochemistry of the volcanic rocks in areas which are fertile with respect to Ni-Cu-PGE deposits and areas which are barren may have implications for ore prospecting in other LIPs around the world. Herzberg, C. & Asimow, P.D. 2008. Petrology of some oceanic island basalts: PRIMELT2.XLS software for primary magma calculation. Geochemistry Geophysics Geosystems 9, doi: 10.1029/2008GC002057.

Petrological, geochemical and isotopic characteristics of lignite and calcified lignite from mining area Pesje, Velenje Basin, Slovenia

NASA Astrophysics Data System (ADS)

Vrabec, Mirijam; Markič, Miloš; Vrabec, Marko; Jaćimović, Radojko; Kanduč, Tjaša

2014-05-01

Lignite (organic rich) and calcified lignite (inorganic rich) samples from excavation field -50c mining area Pesje, Velenje Basin, Slovenia were investigated. During geological and structural mapping lignite and calcified lignite samples were systematically taken for determination of their petrological, geochemical and isotopic characteristics. Lignite is composed of fine detritical gelified matrix. At least five different types of calcified lignite were recognized forming laminations, calcifications after wood, petrified wood and complete replacements of lignite with carbonate. All measured parameters so far indicate geochemical processes during sedimentation of the Velenej Basin. After macroscopic description samples were split to organic and inorganic component (Ward, 1984) and powdered in an agate mortar for geochemical and isotopic analyses. Major and trace elements (As, B, Ba, Cd, Co, Cr, Cu, Hg, Mn, Mo, Sb, Se, Th, U, Zn) in these samples were determined by instrumental neutron activation analysis (INAA) using k-0 standardization method (Jaćimović et al, 2002). The isotopic composition of carbon and nitrogen was determined using a Europa 20-20 continuous flow IRMS ANCA-SL preparation module. A 1 mg amount of a sample was weighed in a tin capsule for carbon and 10 mg for nitrogen analysis. Samples for carbon analyses were pretreated with 1 M HCl to remove carbonates. Carbonate samples from carbonate-rich strata and calcified xylite were first roasted at 450 deg C (Krantz et al., 1987). Three miligrams of carbonate sample was transformed into CO2 by reaction with anhydrous H3PO4 at 55 deg C under vacuum (McCrea, 1950) and measured with GV 2003 isotope ratio mass spectrometer. Measured isotopic composition of oxygen as VPDB values was recalculated to the VSMOW reference standard to enable the comparison with data from other coal basins. SEM/EDXS of carbonate rich sediments was performed with JEOL JSM 5800 electron microanalyzer scanning electron microscope energy dispersive X-ray spectroscopy at the Department of Ceramics at the Jožef Stefan Institute. Geochemical characteristics of major and trace elements indicate that the values of major and trace elements are comparable to world average coal (Zhang et al., 2004). Isotopic composition of carbon and isotopic composition of nitrogen of investigated samples indicate values from to -29.4o to -23.7o and 1.8o to 5.9o respectively. Lower value of isotopic composition of carbon indicates higher gelification (values up to -29.4) and higher value of isotopic composition of nitrogen (values up to 5.9) indicate higher mineralization. The results of SEM/EDXS microscopy revealed that in calcified lignite chemical composition of calcite prevails. Traces of diagenetic pyrite were also found, indicating localized anoxic conditions during sedimentation. Values of isotopic composition of CCaCO3 range from -2 to +13 and indicate temperature of precipitation from 17.3 to 35 deg C, which is similar to results obtained in previous studies (Kanduč et al., 2012). References Krantz, D.E., Williams, D.F., Jones, D.S., 1987: Ecological and paleoenvironmental information using stable isotope profiles from living and fossil mollusks. Palaeogeography, Palaeoclimatology, Palaeoecology 58, 249-266. Kanduč T., Markič M., Zavšek S., McIntosh J. 2012: carbon cycling in the Pliocene Velenje Coal Basin, Slovenia, inferred from stable carbon isotopes. International Journal of Coal Geology 89, 70-83. Jaćimović, R., Lazaru, A., Mihajlović, D., Ilić, R., Stafilov, T., 2002: Determination of major and trace elements in some minerals by k0-instrumental neutron activation analysis. Journal of Radioanalytical Nuclear Chemistry, 253, 427-434. McCrea, JM., 1950. On the isotopic chemistry of carbonates and a paleotemperature scale. Journal of Chemical Physics 18, 849. Ward C.R. (Ed.), 1984: Coal Geology and Coal Technology. Black-well, Oxford, 345 pp. Zhang J.Y., Zheng C.G., Ren D.Y., Chou C.L., Zheng R.S., Wang Z.P., Zhao F. H., Ge Y.T. 2004: Distribution of potentially hazardous trace elements in coals from Shoxi provinces, China. Fuel 83: 129-135.

An internally consistent inverse model to calculate ridge-axis hydrothermal fluxes

NASA Astrophysics Data System (ADS)

Coogan, L. A.; Dosso, S.

2010-12-01

Fluid and chemical fluxes from high-temperature, on-axis, hydrothermal systems at mid-ocean ridges have been estimated in a number of ways. These generally use simple mass balances based on either vent fluid compositions or the compositions of altered sheeted dikes. Here we combine these approaches in an internally consistent model. Seawater is assumed to enter the crust and react with the sheeted dike complex at high temperatures. Major element fluxes for both the rock and fluid are calculated from balanced stoichiometric reactions. These reactions include end-member components of the minerals plagioclase, pyroxene, amphibole, chlorite and epidote along with pure anhydrite, quartz, pyrite, pyrrhotite, titanite, magnetite, ilmenite and ulvospinel and the fluid species H2O, Mg2+, Ca2+, Fe2+, Na+, Si4+, H2S, H+ and H2. Trace element abundances (Li, B, K, Rb, Cs, Sr, Ba, U, Tl, Mn, Cu, Zn, Co, Ni, Pb and Os) and isotopic ratios (Li, B, O, Sr, Tl, Os) are calculated from simple mass balance of a fluid-rock reaction. A fraction of the Cu, Zn, Pb, Co, Ni, Os and Mn in the fluid after fluid-rock reaction is allowed to precipitate during discharge before the fluid reaches the seafloor. S-isotopes are tied to mineralogical reactions involving S-bearing phases. The free parameters in the model are the amounts of each mineralogical reaction that occurs, the amounts of the metals precipitated during discharge, and the water-to-rock ratio. These model parameters, and their uncertainties, are constrained by: (i) mineral abundances and mineral major element compositions in altered dikes from ODP Hole 504B and the Pito and Hess Deep tectonic windows (EPR crust); (ii) changes in dike bulk-rock trace element and isotopic compositions from these locations relative to fresh MORB glass compositions; and (iii) published vent fluid compositions from basalt-hosted high-temperature ridge axis hydrothermal systems. Using a numerical inversion algorithm, the probability density of different model parameter sets has been computed and thus the probability of different fluid and chemical fluxes. Most data can be fit by the model within their uncertainty. The entire dataset is best-fit with a water-to-rock mass ratio between 1.3 and 2.1 (~1 to 1.5 x10**13 kg yr-1) implying a substantial fraction of the magmatic (latent) heat available to drive the axial hydrothermal system is extracted by these systems. Many element fluxes are better constrained than in previous studies (e.g., Sr: 2 to 7 x10**8 moles yr-1; Ca: 2 to 7 x10**11 moles yr-1). Future developments will use experimental data to further constrain the model.

Zn and Cu isotopes as tracers of anthropogenic contamination in a sediment core from an urban lake

USGS Publications Warehouse

Thapalia, Anita; Borrok, David M.; Van Metre, Peter C.; Musgrove, MaryLynn; Landa, Edward R.

2010-01-01

In this work, we use stable Zn and Cu isotopes to identify the sources and timing of the deposition of these metals in a sediment core from Lake Ballinger near Seattle, Washington, USA. The base of the Lake Ballinger core predates settlement in the region, while the upper sections record the effects of atmospheric emissions from a nearby smelter and rapid urbanization of the watershed. δ66Zn and δ65Cu varied by 0.50‰ and 0.29‰, respectively, over the 500 year core record. Isotopic changes were correlated with the presmelter period (∼1450 to 1900 with δ66Zn = +0.39‰ ± 0.09‰ and δ65Cu = +0.77‰ ± 0.06‰), period of smelter operation (1900 to 1985 with δ66Zn = +0.14 ± 0.06‰ and δ65Cu = +0.94 ± 0.10‰), and postsmelting/stable urban land use period (post 1985 with δ66Zn = 0.00 ± 0.10‰ and δ65Cu = +0.82‰ ± 0.12‰). Rapid early urbanization during the post World War II era increased metal loading to the lake but did not significantly alter the δ66Zn and δ65Cu, suggesting that increased metal loads during this time were derived mainly from mobilization of historically contaminated soils. Urban sources of Cu and Zn were dominant since the smelter closed in the 1980s, and the δ66Zn measured in tire samples suggests tire wear is a likely source of Zn.

Trace metal inventories and lead isotopic composition chronicle a forest fire's remobilization of industrial contaminants deposited in the angeles national forest.

PubMed

Odigie, Kingsley O; Flegal, A Russell

2014-01-01

The amounts of labile trace metals: [Co] (3 to 11 µg g-1), [Cu] (15 to 69 µg g-1), [Ni] (6 to 15 µg g-1), [Pb] (7 to 42 µg g-1), and [Zn] (65 to 500 µg g-1) in ash collected from the 2012 Williams Fire in Los Angeles, California attest to the role of fires in remobilizing industrial metals deposited in forests. These remobilized trace metals may be dispersed by winds, increasing human exposures, and they may be deposited in water bodies, increasing exposures in aquatic ecosystems. Correlations between the concentrations of these trace metals, normalized to Fe, in ash from the fire suggest that Co, Cu, and Ni in most of those samples were predominantly from natural sources, whereas Pb and Zn were enriched in some ash samples. The predominantly anthropogenic source of excess Pb in the ash was further demonstrated by its isotopic ratios (208Pb/207Pb: 206Pb/207Pb) that fell between those of natural Pb and leaded gasoline sold in California during the previous century. These analyses substantiate current human and environmental health concerns with the pyrogenic remobilization of toxic metals, which are compounded by projections of increases in the intensity and frequency of wildfires associated with climate change.

Persistent Pb Pollution in Central East Antarctic Snow: A Retrospective Assessment of Sources and Control Policy Implications.

PubMed

Chang, Chaewon; Han, Changhee; Han, Yeongcheol; Hur, Soon Do; Lee, Sanghee; Motoyama, Hideaki; Hou, Shugui; Hong, Sungmin

2016-11-15

Well-defined variations in the enrichments and isotopic compositions of Pb have been observed in snow from Dome Fuji and Dome A in the central East Antarctic Plateau (EAP) over the past few decades. The Pb isotopic fingerprints indicate that the rapid increase in Pb enrichments from the mid-1970s, reaching a peak in ∼1980, is due to the massive use of leaded gasoline in northern South America, especially Brazil. Since then, they show a continuous decline, mostly due to the significant removal of the Pb additives from gasoline in Brazil in the 1980s and, subsequently, in Argentina and Chile in the 1990s. After the phase-out of Pb in gasoline, Cu smelting in Chile has become the major source of Pb, contributing ∼90% to the total Pb emissions in northern South America in 2005. Nevertheless, Pb pollution in the central EAP declined substantially until recently as a result of the regulatory efforts to curb toxic trace metal emissions from the Cu industry in Chile. However, more than 90% of the Pb in the most remote places on Earth are still of anthropogenic origin, highlighting the need for the continuation of environmental regulations for the further reduction of Pb emissions.

The Shaw chondrite. I - The case of the missing metal

NASA Technical Reports Server (NTRS)

Rambaldi, E. R.; Larimer, J. W.

1976-01-01

The mineralogy as well as the elemental and isotopic composition of the Shaw meteorite indicate that it is a highly metamorphosed L-group chondrite which has lost a portion of its metal and sulfide. The metal which remains has an unusual composition relative to that in other L-group chondrites. It is enriched in Ga, Ge, Ir, Mo, Os, Pt, Re, and Ru but depleted in As, Au, Cu, and Sb. A comparison of the relative enrichments and depletions in Shaw with those observed in San Cristobal, the extreme end-member of group IAB iron meteorites, shows that the metal phases in these two meteorites have complementary compositions. This implies that the metal in Shaw represents the residual solid of a partial melting process while the missing metal, which drained away, may have gone to form an iron meteorite, like San Cristobal.

Microscale Variations in the 13C Content of the Murchison Meteorite

NASA Astrophysics Data System (ADS)

Romanek, C.; Gibson, E.; Socki, R.; Burkett, P. J.

1993-07-01

Heretofore unresolved micrometer-scale carbon isotopic zonation in the Murchison meteorite (CM3) is documented using a laser microprobe mass spectrometer. High-resolution isotopic gradients and heterogeneities between high- and low-temperature textural components help to constrain the processes that have shaped the physiochemical character of this carbonaceous chondrite. Previous bulk samples of Murchison yield an average delta ^13C value of - 5.7 +/- 4.3 per mil [1] while individual components such as micrometer-sized mineral separates (e.g., C(sub)graphite , C(sub)diamond, and SiC), acid- soluble extracts (e.g., CaCO3 and polar hydrocarbons), and insoluble residues (e.g., polycyclic aromatic hydrocarbons) are isotopically diverse (delta ^13C of -1000 to 29,000 per mil). While these studies shed light on the origin and occurrence of C-bearing phases, they fail to constrain intrinsic spatial isotopic heterogeneities. The power of the laser microprobe lies in the fact that in situ chemical and isotopic compositions are measured simultaneously for volatiles extracted from extremely small sample volumes (i.e., 0.025 mm^3 for 5 wt% C). Nd-YAG laser irradiation (1.06 micrometers) is directed onto texturally defined targets (>=50 micrometers wide) from which solid material is volatilized. Condensible gaseous phases are collected in a variable-temperature cold trap while the more volatile species (CH4 and CO) are quantified using an ion trap mass spectrometer. All gases are then converted to CO2 in a CuO furnace (containing Pt) held at 600 degrees C and analyzed for carbon and oxygen isotope ratios. The concentration and isotopic composition of condensed species are determined by stepped sublimation of unstable components and conversion to CO2. Preliminary isotopic analyses of the total volatile C content (i.e., bulk microanalysis) from distinct textural components at least 0.05 mm^3 in volume are described below. The most ^13C-depleted components within Murchison reside within the cores of chondrules and/or aggregates. Three typical cores were analyzed, with an average bulk composition of -21.0 +/- 0.5 per mil (n = 7). The bulk ^13C content of C-bearing phases increases monotonically outward in all directions within 100 to 200 micrometers of each core (i.e., within dust mantles) to a constant matrix value of -12.5 +/- 0.5 per mil (n = 40). The most isotopically enriched textural component found in Murchison is a regolith breccia clast without chondrules that has an average bulk delta ^13C value of -10 +/-0.5 per mil (n = 5). The clast was originally detectable only under cathodoluminescence, but with the aid of the laser microprobe it is now characterized by an unusually low volatile content and enriched ^13C composition. In general, the most isotopically enriched components also produce the lowest yield of gas (normalized to sampling volume). This trend of isotopic enrichment from chondrule to matrix has been documented previously for oxygen isotopes in carbonaceous chondrites [2]. Carbon isotopic gradients and heterogeneities within Murchison reflect fundamental changes in the chemical speciation and/or isotopic content of the main C-bearing components (i.e., acid-soluble and insoluble hydrocarbon fractions) within the meteorite. Perhaps core interiors and dust mantles are responding to environmental changes reflected in the speciation of C-bearing species distributed within the solar nebula or the parent body. Inverse correlations between hydrocarbon atomic mass number and ^13C abundance in the acid-soluble [3] and insoluble residues [4] of Murchison have been documented. Alternatively, micrometer-scale isotopic gradients may reflect fundamental changes in the isotopic composition of individual C-bearing species through time. Enrichments may represent kinetically controlled processes related to hydrocarbon formation. In contrast, assuming an equilibrium fractionation mechanism, isotopic enrichments may record a temperature-dependent component to hydrocarbon delta ^13C values. These opposing alternatives will be discussed in light of the isotopic composition of individual C-bearing components volatilized from tightly constrained sample volumes within Murchison. References: [1] Kerridge J. F. (1985) GCA, 49, 1707-1714. [2] Clayton R. N. and Mayeda T. K. (1984) EPSL, 67, 151-161. [3] Yuen G. et al. (1984) Nature, 307, 254. [4] Gilmour I. et al. (1991) Meteoritics, 26, 337-338.

Isotopic evidence for omnivory among European cave bears: Late Pleistocene Ursus spelaeus from the Peştera cu Oase, Romania

PubMed Central

Richards, Michael P.; Pacher, Martina; Stiller, Mathias; Quilès, Jérôme; Hofreiter, Michael; Constantin, Silviu; Zilhão, João; Trinkaus, Erik

2008-01-01

Previous bone collagen carbon and nitrogen isotopic studies of Late Pleistocene European cave bears (Ursus spelaeus) have shown that these bears frequently had low nitrogen isotope values, similar to those of herbivores and indicating either unusual physiology related to hibernation or a herbivorous diet. Isotopic analysis of animal bone from the Peştera cu Oase (Cave with Bones), Romania, shows that most of its cave bears had higher nitrogen isotope values than the associated herbivores and were, therefore, omnivorous. The Oase bears are securely identified as cave bears by both their morphology and DNA sequences. Although many cave bear populations may have behaved like herbivores, the Oase isotopic data demonstrate that cave bears were capable of altering their diets to become omnivores or even carnivores. These data therefore broaden the dietary profile of U. spelaeus and raise questions about the nature of the carnivore guild in Pleistocene Europe. PMID:18187577

The novel approach to the biomonitor survey using one- and two-dimensional Kohonen networks.

PubMed

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.

The case for metamorphic base metal mineralization: pyrite chemical, Cu and S isotope data from the Cu-Zn deposit at Kupferberg in Bavaria, Germany

NASA Astrophysics Data System (ADS)

Höhn, S.; Frimmel, H. E.; Debaille, V.; Pašava, J.; Kuulmann, L.; Debouge, W.

2017-12-01

The stratiform Cu-Zn sulfide deposit at Kupferberg in Germany represents Bavaria's largest historic base metal producer. The deposit is hosted by Early Paleozoic volcano-sedimentary strata at the margin of a high-grade allochthonous metamorphic complex. The present paper reports on the first Cu and S isotope data as well as trace element analyses of pyrite from this unusual deposit. The new data point to syn-orogenic mineralization that was driven by metamorphic fluids during nappe emplacement. Primary Cu ore occurs as texturally late chalcopyrite within stratiform laminated pyrite in black shale in two different tectonostratigraphic units of very low and low metamorphic grade, respectively, that were juxtaposed during the Variscan orogeny. Trace element contents of different pyrite types suggest the presence of at least one hydrothermal pyrite generation (mean Co/Ni = 35), with the other pyrite types being syn-sedimentary/early diagenetic (mean Co/Ni = 3.7). Copper isotope analyses yielded a narrow δ65Cu range of -0.26 to 0.36‰ for all ore types suggesting a hypogene origin for the principal chalcopyrite mineralization. The ore lenses in the two different tectonostratigraphic units differ with regard to their δ34S values, but little difference exists between poorly and strongly mineralized domains within a given locality. A genetic model is proposed in which syn-sedimentary/early diagenetic pyrite with subordinate chalcopyrite and sphalerite formed in black shale beds in the two different stratigraphic units, followed by late-tectonic strata-internal, hydrothermal mobilization of Fe, Cu, and Zn during syn-orogenic thrusting, which concentrated especially Cu to ore grade. In agreement with this model, Cu distribution in stream sediments in this region shows distinct enrichments bound to the margin of the allochthonous complex. Thus, Kupferberg can be considered a rare example of a syn-orogenic Cu deposit with the Cu probably being derived from syn-sedimentary/early diagenetic pyrite contained in Early Paleozoic shale units.

Automated production of 124I and 64Cu using IBA Terimo and Pinctada metal electroplating and processing modules

NASA Astrophysics Data System (ADS)

Poniger, S. S.; Tochon-Danguy, H. J.; Panopoulos, H. P.; O'Keefe, G. J.; Peake, D.; Rasool, R.; Scott, A. M.

2012-12-01

There is worldwide growing interest for the production of long-lived positron emitters for molecular imaging and the development of novel immuno-PET techniques for drugs discovery. The desire to produce solid target isotopes in Australia has significantly increased over the years and several research projects for labelling of peptides, proteins and biomolecules, including labelling of recombinant antibodies has been limited due to the availability of suitable isotopes. This has led to the recent installation and commissioning of a new lab dedicated to fully automated solid target isotope production, including 124I, 64Cu, 89Zr and 86Y.

Uranium-lead dating of hydrothermal zircon and monazite from the Sin Quyen Fe-Cu-REE-Au-(U) deposit, northwestern Vietnam

NASA Astrophysics Data System (ADS)

Li, Xiao-Chun; Zhou, Mei-Fu; Chen, Wei Terry; Zhao, Xin-Fu; Tran, MyDung

2018-03-01

The Sin Quyen deposit in northwestern Vietnam contains economic concentrations of Cu, Au and LREE, and sub-economic concentration of U. In this deposit, massive and banded replacement ores are hosted in Neoproterozoic metapelite. The paragenetic sequence includes sodic alteration (stage I), calcic-potassic alteration and associated Fe-REE-(U) mineralization (stage II), Cu-Au mineralization (stage III), and sulfide-(quartz-carbonate) veins (stage IV). The Sin Quyen deposit experienced an extensive post-ore metamorphic overprint, which makes it difficult to precisely determine the mineralization age. In this study, zircon and monazite U-Pb geochronometers and the Rb-Sr isochron method are used to constrain the timing of mineralization. Zircon grains in the ore are closely intergrown or texturally associated with hydrothermal minerals of stage II (e.g., garnet, allanite, and hedenbergite). They may contain primary fluid inclusions and display irregular zoning in cathodoluminescence (CL) images. Zircon grains are rich in U (688 to 2902 ppm) and poor in Th (0.2 to 2.9 ppm). Their δ18OV-SMOW values range from 11.9 to 14.0‰, higher than those of typical magmatic zircon. These textural and compositional features imply that zircon precipitated from 18O- and U-rich hydrothermal fluids, coeval with the minerals of stage II. Monazite occurs in close association with stage II magnetite and allanite and has low contents of Th (<2700 ppm), indicative of a hydrothermal origin. Hydrothermal zircon and monazite have indistinguishable U-Pb ages of 841 ± 12 and 836 ± 18 Ma, respectively, representing the timing of Fe-REE mineralization. There is no direct isotopic constraint on the timing of the Cu-Au mineralization, but geological observations suggest that the Cu-Au and Fe-REE ores most likely formed within a single evolved hydrothermal process. In the plot of 87Rb/86Sr vs. 87Sr/86Sr, the composition of bulk-ore and biotite separates from ore lie along a reference line for 30 Ma, which is consistent with the timing of metamorphism in the region. The mineralization age of the Sin Quyen deposit falls within the overall age range (740 to 860 Ma) of the regional Neoproterozoic igneous rocks. This temporal linkage, in combination with the magmatic-like sulfur isotopes of sulfide minerals (δ34SV-CDT = -0.8 to 3.1), indicates that the mineralization may have a close genetic association with the Neoproterozoic igneous activity.

Effective load transfer by a chromium carbide nanostructure in a multi-walled carbon nanotube/copper matrix composite

NASA Astrophysics Data System (ADS)

Cho, Seungchan; Kikuchi, Keiko; Kawasaki, Akira; Kwon, Hansang; Kim, Yangdo

2012-08-01

Multi-walled carbon nanotube (MWCNT) reinforced copper (Cu) matrix composites, which exhibit chromium (Cr) carbide nanostructures at the MWCNT/Cu interface, were prepared through a carbide formation using CuCr alloy powder. The fully densified and oriented MWCNTs dispersed throughout the composites were prepared using spark plasma sintering (SPS) followed by hot extrusion. The tensile strengths of the MWCNT/CuCr composites increased with increasing MWCNTs content, while the tensile strength of MWCNT/Cu composite decreased from that of monolithic Cu. The enhanced tensile strength of the MWCNT/CuCr composites is a result of possible load-transfer mechanisms of the interfacial Cr carbide nanostructures. The multi-wall failure of MWCNTs observed in the fracture surface of the MWCNT/CuCr composites indicates an improvement in the load-bearing capacity of the MWCNTs. This result shows that the Cr carbide nanostructures effectively transferred the tensile load to the MWCNTs during fracture through carbide nanostructure formation in the MWCNT/Cu composite.

Ultraviolet optical absorptions of semiconducting copper phosphate glasses

NASA Technical Reports Server (NTRS)

Bae, Byeong-Soo; Weinberg, Michael C.

1993-01-01

Results are presented of a quantitative investigation of the change in UV optical absorption in semiconducting copper phosphate glasses with batch compositions of 40, 50, and 55 percent CuO, as a function of the Cu(2+)/Cu(total) ratio in the glasses for each glass composition. It was found that optical energy gap, E(opt), of copper phosphate glass is a function of both glass composition and Cu(2+)/Cu(total) ratio in the glass. E(opt) increases as the CuO content for fixed Cu(2+)/Cu(total) ratio and the Cu(2+)/Cu(total) ratio for fixed glass composition are reduced.

Contrasting Cu-Au and Sn-W Granite Metallogeny through the Zircon Geochemical and Isotopic Record

NASA Astrophysics Data System (ADS)

Gardiner, Nicholas; Hawkesworth, Chris; Robb, Laurence; Whitehouse, Martin; Roberts, Nick; Kirkland, Chris

2017-04-01

Magmatic genesis and evolution - mediated by geodynamic setting - exert a primary control on the propensity of granites to be metal fertile. A revolution in our understanding of these petrogenetic processes has been made through a range of mineral-based tools, most notably the common accessory mineral zircon. There is consequently considerable interest in whether the geochemical and isotopic compositions of zircon can be applied to metallogenic problems. The paired magmatic belts of Myanmar have broadly contrasting metallogenic affinities (Sn-W versus Cu-Au), and are interpreted to have formed on the accretionary margin of the subducting Neo-Tethys Ocean. They therefore present the opportunity to geochemically compare and contrast the zircon compositions in two end-member types of granite-hosted mineral deposits generated in collisional settings. We present an integrated zircon isotope (U-Pb, Lu-Hf, O) and trace element dataset that fingerprint: (a) source; (b) redox conditions; and (c) degree of fractionation. These variables all impact on magma fertility, and our key question to address is whether they can be reliably traced and calibrated within the Myanmar zircon record. Granitoid-hosted zircons from the I-type copper arc have juvenile ɛHf (+7 to +12) and mantle-like δ18O (5.3 ‰), whereas zircons from the S-type tin belt have low ɛHf (-7 to -13) and heavier δ18O (6.2-7.7 ‰). Plotting Hf versus U/Yb reaffirms that the tin belt magmas contain greater crustal contributions than the copper arc rocks. Links between whole rock Rb/Sr and zircon Eu/Eu* highlights that the latter can be used to monitor magma fractionation in systems that crystallize plagioclase (low Sr/Y). Ce/Ce* and Eu/Eu* in zircon are thus sensitive to redox and fractionation respectively, and can be used to evaluate the sensitivity of zircons to the metallogenic affinity of their host rocks. Tin contents that exceed the solubility limit are required in order to make a magmatic-hydrothermal deposit, and empirical observations suggest that this threshold may be marked by zircon Eu/Eu* values of ca. < 0.08. The isotope and trace element signatures of both magmatic and detrital zircons can be developed into a useful exploration tool.

Contamination history of lead and other trace metals reconstructed from an urban winter pond in the Eastern Mediterranean coast (Israel).

PubMed

Zohar, I; Bookman, R; Levin, N; de Stigter, H; Teutsch, N

2014-12-02

Pollution history of Pb and other trace metals was reconstructed for the first time for the Eastern Mediterranean, from a small urban winter pond (Dora, Netanya), located at the densely populated coastal plain of Israel. An integrated approach including geochemical, sedimentological, and historical analyses was employed to study sediments from the center of the pond. Profiles of metal concentrations (Pb, Zn, V, Ni, Cu, Cr, Co, Cd, and Hg) and Pb isotopic composition denote two main eras of pre- and post-19th century. The deeper sediment is characterized by low concentrations and relatively constant 206Pb/207Pb (around 1.20), similar to natural Pb sources, with slight indications of ancient anthropogenic activity. The upper sediment displays an upward increase in trace metal concentrations, with the highest enrichment factor for Pb (18.4). Lead fluxes and isotopic composition point to national/regional petrol-Pb emissions as the major contributor to Pb contamination, overwhelming other potential local and transboundary sources. Traffic-related metals are correlated with Pb, emphasizing the polluting inputs of traffic. The Hg profile, however, implies global pollution rather than local sources.

A novel copper/polydimethiylsiloxane nanocomposite for copper-containing intrauterine contraceptive devices.

PubMed

Xu, X X; Ding, M H; Zhang, J X; Zheng, W; Li, L; Zheng, Y F

2013-11-01

In this article, a novel composite of copper (Cu) nanoparticles and polydimethiylsiloxane (PDMS) has been prepared and investigated for the potential application in Cu-containing intrauterine device. The Cu/PDMS composite with various mass fraction of Cu nanoparticles was fabricated via the hot vulcanizing process. The chemical structures and surface morphologies of the Cu/PDMS composites were characterized confirming the physical interaction between Cu nanoparticles and PDMS. The surface morphology observation using scanning electron microscope and atomic force microscope showed the agglomeration of Cu nanoparticles in PDMS matrix and the distribution of the agglomerations was more uniform with increased amount of Cu nanoparticles. The cupric ion release behaviors of the Cu/PDMS composites with different amounts of Cu nanoparticles were investigated in simulated uterine fluid at 37°C for 150 days. The corrosion morphologies of the Cu/PDMS composites were also characterized. Both the burst release rate of the cupric ion in the first few days and the steady release rate after 30-day immersion were improved. The cytotoxicity test has been done for the Cu/PDMS composites. Copyright © 2013 Wiley Periodicals, Inc.

Compression Properties and Electrical Conductivity of In-Situ 20 vol.% Nano-Sized TiCx/Cu Composites with Different Particle Size and Morphology

PubMed Central

Zhang, Dongdong; Bai, Fang; Sun, Liping; Wang, Yong; Wang, Jinguo

2017-01-01

The compression properties and electrical conductivity of in-situ 20 vol.% nano-sized TiCx/Cu composites fabricated via combustion synthesis and hot press in Cu-Ti-CNTs system at various particles size and morphology were investigated. Cubic-TiCx/Cu composite had higher ultimate compression strength (σUCS), yield strength (σ0.2), and electric conductivity, compared with those of spherical-TiCx/Cu composite. The σUCS, σ0.2, and electrical conductivity of cubic-TiCx/Cu composite increased by 4.37%, 20.7%, and 17.8% compared with those of spherical-TiCx/Cu composite (526 MPa, 183 MPa, and 55.6% International Annealed Copper Standard, IACS). Spherical-TiCx/Cu composite with average particle size of ~94 nm exhibited higher ultimate compression strength, yield strength, and electrical conductivity compared with those of spherical-TiCx/Cu composite with 46 nm in size. The σUCS, σ0.2, and electrical conductivity of spherical-TiCx/Cu composite with average size of ~94 nm in size increased by 17.8%, 33.9%, and 62.5% compared with those of spherical-TiCx/Cu composite (417 MPa, 121 MPa, and 40.3% IACS) with particle size of 49 nm, respectively. Cubic-shaped TiCx particles with sharp corners and edges led to stress/strain localization, which enhanced the compression strength of the composites. The agglomeration of spherical-TiCx particles with small size led to the compression strength reduction of the composites. PMID:28772859

Geology and reconnaissance stable isotope study of the Oyu Tolgoi porphyry Cu-Au system, South Gobi, Mongolia

USGS Publications Warehouse

Khashgerel, B.-E.; Rye, R.O.; Hedenquist, J.W.; Kavalieris, I.

2006-01-01

The Oyu Tolgoi porphyry Cu-Au system in the South Gobi desert, Mongolia, comprises five deposits that extend over 6 km in a north-northeast-oriented zone. They occur in a middle to late Paleozoic are terrane and are related to Late Devonian quartz monzodiorite intrusions. The Hugo Dummett deposits are the northernmost and deepest, with up to 1,000 m of premineral sedimentary and volcanic cover rock remaining. They are the largest deposits discovered to date and characterized by high-grade copper (>2.5% Cu) and gold (0.5-2 g/t) mineralization associated with intense quartz veining and several phases of quartz monzodiorite intruded into basaltic volcanic host rocks. Sulfide minerals in these deposits are zoned outward from a bornite-dominated core to chalcopyrite, upward to pyrite ?? enargite and covellite at shallower depth. The latter high-sulfidation-state sulfides are hosted by advanced argillic alteration mineral associations. This alteration is restricted mainly to dacitic ash-flow tuff that overlies the basaltic volcanic rock and includes ubiquitous quartz and pyrophyllite, kaolinite, plus late dickite veins, as well as K alunite, Al phosphate-sulfate minerals, zunyite, diaspore, topaz, corundum, and andalusite. A reconnaissance oxygen-hydrogen and sulfur isotope study was undertaken to investigate the origin of several characteristic alteration minerals in the Oyu Tolgoi system, with particular emphasis on the Hugo Dummett deposits. Based on the isotopic composition of O, H, and S (??18O(SO4) = 8.8-20.1???, ??D = -73 to -43???, ??34S = 9.8-17.9???), the alunite formed from condensation of magmatic vapor that ascended to the upper parts of the porphyry hydrothermal system, without involvement of significant amounts of meteoric water. The isotopic data indicate that pyrophyllite (??18O = 6.5-10.9???, ??D = -90 to -106???) formed from a magmatic fluid with a component of meteoric water. Muscovite associated with quartz monzodiorite intrusions occurs in the core of the Hugo Dummett deposits, and isotopic data (??18O = 3.0-9.0???, ??D = -101 to -116%o) show it formed from a magmatic fluid with water similar in composition to that which formed the pyrophyllite. Mg chlorite (??18O = 5.5???, ??D = -126???) is a widespread mineral retrograde after hydrothermal biotite and may have formed from fluids similar to those related to the muscovite during cooling of the porphyry system. By contrast, paragenetically later and postmineralization alteration fluid, which produced dickite (??18O = -4.1 to +3.3???, ??D = -130 to -140???), shows clear evidence for mixing with substantial amounts of meteoric water. Relatively low ??D values (-140???) for this meteoric water component may indicate that its source was at high elevations. The geologic structure, nature of alteration, styles of mineralization, and stable isotope data indicate that the Oyu Tolgoi deposits constitute a typical porphyry system formed in an island-arc setting. The outward zonation of sulfide minerals for the Hugo Dummett deposits, from a bornite-dominated core to chalcopyrite and pyrite-enargite, can be interpreted to be related to a cooling magmatic hydrothermal system which transgressed outward over enclosing advanced argillic alteration. This resulted in some unusual alteration and sulfide parageneses, such as topaz, or pyrite, enargite, and tennantite, entrained by high-grade bornite. ?? 2006 by Economic Geology.

Fluid sources and metallogenesis in the Blackbird Co-Cu-Au-Bi-Y-REE district, Idaho, U.S.A.: Insights from major-element and boron isotopic compositions of tourmaline

USGS Publications Warehouse

Trumbull, Robert B.; Slack, John F.; Krienitz, M.-S.; Belkin, Harvey E.; Wiedenbeck, M.

2011-01-01

Tourmaline is a widespread mineral in the Mesoproterozoic Blackbird Co–Cu–Au–Bi–Y–REE district, Idaho, where it occurs in both mineralized zones and wallrocks. We report here major-element and B-isotope compositions of tourmaline from stratabound sulfide deposits and their metasedimentary wallrocks, from mineralized and barren pipes of tourmaline breccia, from late barren quartz veins, and from Mesoproterozoic granite. The tourmalines are aluminous, intermediate in the schorl–dravite series, with Fe/(Fe + Mg) values of 0.30 to 0.85, and 10 to 50% X-site vacancies. Compositional zoning is prominent only in tourmaline from breccias and quartz veins; crystal rims are enriched in Mg, Ca and Ti, and depleted in Fe and Al relative to cores. The chemical composition of tourmaline does not correlate with the presence or absence of mineralization. The δ11B values fall into two groups. Isotopically light tourmaline (−21.7 to −7.6‰) occurs in unmineralized samples from wallrocks, late quartz veins and Mesoproterozoic granite, whereas heavy tourmaline (−6.9 to +3.2‰) is spatially associated with mineralization (stratabound and breccia-hosted), and is also found in barren breccia. At an inferred temperature of 300°C, boron in the hydrothermal fluid associated with mineralization had δ11B values of −3 to +7‰. The high end of this range indicates a marine source of the boron. A likely scenario involves leaching of boron principally from marine carbonate beds or B-bearing evaporites in Mesoproterozoic strata of the region. The δ11B values of the isotopically light tourmaline in the sulfide deposits are attributed to recrystallization during Cretaceous metamorphism, superimposed on a light boron component derived from footwall siliciclastic sediments (e.g., marine clays) during Mesoproterozoic mineralization, and possibly a minor component of light boron from a magmatic–hydrothermal fluid. The metal association of Bi–Be–Y–REE in the Blackbird ores suggests some magmatic input, but involvement of granite-derived fluids cannot be conclusively established from the present database.

U-Pb (zircon) and geochemical constraints on the age, origin, and evolution of Paleozoic arc magmas in the Oyu Tolgoi porphyry Cu-Au district, southern Mongolia

USGS Publications Warehouse

Wainwright, A.J.; Tosdal, R.M.; Wooden, J.L.; Mazdab, F.K.; Friedman, R.M.

2011-01-01

Uranium-Pb (zircon) ages are linked with geochemical data for porphyry intrusions associated with giant porphyry Cu-Au systems at Oyu Tolgoi to place those rocks within the petrochemical framework of Devonian and Carboniferous rocks of southern Mongolia. In this part of the Gurvansayhan terrane within the Central Asian Orogenic Belt, the transition from Devonian tholeiitic marine rocks to unconformably overlying Carboniferous calc-alkaline subaerial to shallow marine volcanic rocks reflects volcanic arc thickening and maturation. Radiogenic Nd and Pb isotopic compositions (??Nd(t) range from +3.1 to +7.5 and 206Pb/204Pb values for feldspars range from 17.97 to 18.72), as well as low high-field strength element (HFSE) contents of most rocks (mafic rocks typically have <1.5% TiO2) are consistent with magma derivation from depleted mantle in an intra-oceanic volcanic arc. The Late Devonian and Carboniferous felsic rocks are dominantly medium- to high-K calc-alkaline and characterized by a decrease in Sr/Y ratios through time, with the Carboniferous rocks being more felsic than those of Devonian age. Porphyry Cu-Au related intrusions were emplaced in the Late Devonian during the transition from tholeiitic to calc-alkaline arc magmatism. Uranium-Pb (zircon) geochronology indicates that the Late Devonian pre- to syn-mineral quartz monzodiorite intrusions associated with the porphyry Cu-Au deposits are ~372Ma, whereas granodiorite intrusions that post-date major shortening and are associated with less well-developed porphyry Cu-Au mineralization are ~366Ma. Trace element geochemistry of zircons in the Late Devonian intrusions associated with the porphyry Cu-Au systems contain distinct Th/U and Yb/Gd ratios, as well as Hf and Y concentrations that reflect mixing of magma of distinct compositions. These characteristics are missing in the unmineralized Carboniferous intrusions. High Sr/Y and evidence for magma mixing in syn- to late-mineral intrusions distinguish the Late Devonian rocks associated with giant Cu-Au deposits from younger magmatic suites in the district. ?? 2010 Elsevier B.V.

Effect of Sn-Ag-Cu on the Improvement of Electromigration Behavior in Sn-58Bi Solder Joint

NASA Astrophysics Data System (ADS)

Wang, Fengjiang; Zhou, Lili; Zhang, Zhijie; Wang, Jiheng; Wang, Xiaojing; Wu, Mingfang

2017-10-01

Reliability issues caused by the formation of a Bi-rich layer at the anode interface usually occurs in the Sn-58Bi eutectic solder joint during electromigration (EM). To improve the EM performance of a Sn-58Bi solder joint, Sn-3.0Ag-0.5Cu solder was introduced into it to produce SnBi-SnAgCu structural or compositional composite joints, and their EM behaviors were investigated with the current density of 1.0 × 104 A/cm2 for different stressing times. The structure of the compositional composite solder joint was obtained by the occurrence of partial or full mixing between Sn-Bi and Sn-Ag-Cu solder with a suitable soldering temperature. In the structural composite joint, melted Sn-Bi was partially mixed with Sn-Ag-Cu solder to produce a Cu/Sn-Bi/Sn-Ag-Cu/Sn-Bi/Cu structure. In the compositional composite joint, full melting and mixing between these two solders occurred to produce a Cu/Sn-Ag-Cu-Bi/Cu structure, in which the solder matrix was a homogeneous structure including Sn, Bi phases, Cu6Sn5 and Ag3Sn IMCs. After current stressing, the EM performance of Sn-Bi solder was obviously improved with the structural or the compositional composite joint. In Sn-58Bi joints, a thick Bi-rich layer was easily produced at the anode interface, and obviously increased with stressing time. However, after current stressing on the structural composite joints, the existence of s Sn-3.0Ag-0.5Cu interlayer between the two Sn-58Bi solders effectively acted as a diffusion barrier and significantly slowed the formation of the Bi-rich layer at the anode side and the IMC thicknesses at the interfaces.

The sources and evolution of mineralising fluids in iron oxide-copper-gold systems, Norrbotten, Sweden: Constraints from Br/Cl ratios and stable Cl isotopes of fluid inclusion leachates

NASA Astrophysics Data System (ADS)

Gleeson, S. A.; Smith, M. P.

2009-10-01

We have analysed the halogen concentrations and chlorine stable isotope composition of fluid inclusion leachates from three spatially associated Fe-oxide ± Cu ± Au mineralising systems in Norrbotten, Sweden. Fluid inclusions in late-stage veins in Fe-oxide-apatite deposits contain saline brines and have a wide range of Br/Cl molar ratios, from 0.2 to 1.1 × 10 -3 and δ 37Cl values from -3.1‰ to -1.0‰. Leachates from saline fluid inclusions from the Greenstone and Porphyry hosted Cu-Au prospects have Br/Cl ratios that range from 0.2 to 0.5 × 10 -3 and δ 37Cl values from -5.6‰ to -1.3‰. Finally, the Cu-Au deposits hosted by the Nautanen Deformation Zone (NDZ) have Br/Cl molar ratios from 0.4 to 1.1 × 10 -3 and δ 37Cl values that range from -2.4‰ to +0.5‰, although the bulk of the data fall within 0‰ ± 0.5‰. The Br/Cl ratios of leachates are consistent with the derivation of salinity from magmatic sources or from the dissolution of halite. Most of the isotopic data from the Fe-oxide-apatite and Greenstone deposits are consistent with a mantle derived source of the chlorine, with the exception of the four samples with the most negative values. The origin of the low δ 37Cl values in these samples is unknown but we suggest that there may have been some modification of the Cl-isotope signature due to fractionation between the mineralising fluids and Cl-rich silicate assemblages found in the alteration haloes around the deposits. If such a process has occurred then a modified crustal source of the chlorine for all the samples cannot be ruled out although the amount of fractionation necessary to generate the low δ 37Cl values would be significantly larger. The source of Cl in the NDZ deposits has a crustal signature, which suggests the Cl in this system may be derived from (meta-) evaporites or from input from crustal melts such as granitic pegmatites of the Lina Suite.

Oxygen isotope effect in disordered underdoped and overdoped La 2-xSr xCu 1-yZn yO 4 superconductors

NASA Astrophysics Data System (ADS)

Naqib, S. H.; Islam, R. S.

2011-04-01

The effect of oxygen isotopic substitution on the superconducting transition temperature has been studied for heavily underdoped and overdoped La 2-xSr xCu 1-yZn yO 4 compounds with different Zn contents in the CuO 2 plane. The effect of Zn on the isotope coefficient, α, was significantly more pronounced in the case of the underdoped ( x = 0.09) compounds compared to the overdoped ( x = 0.22) ones. The variation of α with disorder content can be described quite well within a model based solely on Cooper pair-breaking in the case of the underdoped compounds. This model fails to describe the behavior of α( y) for the overdoped samples, even though Zn still suppresses T c very effectively at this hole (Sr) content, indicating that the Zn induced pair-breaking is still very much at play. We discuss the implications of these findings in details by considering the Zn induced magnetism, stripe correlations, and possible changes in the superconducting order parameter as hole content in the CuO 2 plane, p (≡ x), is varied.

A porous Cu/LDPE composite for copper-containing intrauterine contraceptive devices.

PubMed

Zhang, Weiwei; Xia, Xianping; Qi, Cheng; Xie, Changsheng; Cai, Shuizhou

2012-02-01

To improve the rates of both cupric ion release and the utilization of copper in non-porous copper/low-density polyethylene (Cu/LDPE) composite, a porous Cu/LDPE composite is proposed and developed in the present work. Here 2,5-di-tert-butylhydroquinone was chosen as the porogen, ethyl acetate was chosen as the solvent for extraction, and the porous Cu/LDPE composite was obtained by using injection molding and the particulate leaching method. After any residual ethyl acetate remaining inside the porous Cu/LDPE composite had been removed by vacuum drying, the composite was characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, gas chromatography-mass spectrometry and absorption measurement. For comparison, a non-porous Cu/LDPE composite was also characterized in the same way. The results show that the porous structure was successfully introduced into the polymeric base of the non-porous Cu/LDPE composite, and the porous Cu/LDPE composite is a simple hybrid of copper particles and porous LDPE. The results also show that the introduction of a porous structure can improve the cupric ion release rate of the non-porous Cu/LDPE composite with a certain content of copper particles, indicating that the utilization rate of copper can be improved either the introduction of a porous structure, and that the porous Cu/LDPE composite is another promising material for copper-containing intrauterine devices. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The Fluctuating Bond Model, a Glue for Cuprate Superconductivity?

NASA Astrophysics Data System (ADS)

Newns, Dennis

2008-03-01

Twenty years of research have yet to produce a consensus on the origin of high temperature superconductivity (HTS). The mechanism of HTS - which originates in the CuO2 plane, common to all HTS families - can be constrained by some key experimental facts regarding superconducting and pseudogap behaviors. Superconductivity, involving a Tc of order 100 K, exhibits an unusual d-wave superconducting gap, with Fermi liquid nodal excitations, and an anomalous doping- dependent oxygen isotope shift. A ``pseudogap,'' also with d-symmetry, leads to a dip in the density of states below a characteristic temperature scale T^*, which has a negative isotope shift; we associate the pseudogap with the recently observed spatially inhomogeneous (nanometer- scale) C4 symmetry breaking. The isotope shifts and other evidence imply a key role for oxygen vibrations, but conventional BCS single-phonon coupling is essentially forbidden by symmetry and by the on-site Coulomb interaction U. In a novel approach, we introduce a model based on a strong, local, nonlinear interaction between electrons within the Cu-O-Cu bond in the CuO2 plane, and the oxygen vibrational degrees of freedom, termed the Fluctuating Bond Model (FBM) [D.M. Newns and C.C. Tsuei, Nature Physics 3, 184 (2007)]. In mean field the model predicts a phase manifesting broken C4 symmetry, with a d-type pseudogap, and an upper phase boundary in temperature, with a negative isotope shift, which we identify with T^*. An intrinsic d-wave pairing tendency is found, leading to a transition temperature dome and an anomalous isotope shift similar to that found experimentally. The softening in the oxygen vibrational frequency below Tc, seen in Raman and neutron spectra, has a natural explanation in the FBM. Recent ab initio calculations have been implemented which provide microscopic support for the model.

Variability of Fe isotope compositions of hydrothermal sulfides and oxidation products at mid-ocean ridges

NASA Astrophysics Data System (ADS)

Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Wang, Hao; Li, Zhenggang; Yu, Xing; Bi, Dongwei; He, Yongsheng

2018-04-01

Significant Fe isotopic fractionation occurs during the precipitation and oxidative weathering of modern seafloor hydrothermal sulfides, which has an important impact on the cycling of Fe isotopes in the ocean. This study reports the Fe-isotope compositions of whole-rock sulfides and single-mineral pyrite collected from hydrothermal fields at the South Mid-Atlantic Ridge (SMAR) and the East Pacific Rise (EPR) and discusses the impacts of precipitation and late-stage oxidative weathering of sulfide minerals on Fe isotopic fractionation. The results show large variation in the Fe-isotope compositions of the sulfides from the different hydrothermal fields on the mid-oceanic ridges, indicating that relatively significant isotope fractionation occurs during the sulfide precipitation and oxidative weathering processes. The Fe-isotope compositions of the sulfides from the study area at the SMAR vary across a relatively small range, with an average value of 0.01‰. This Fe-isotope composition is similar to the Fe-isotope composition of mid-oceanic ridge basalt, which suggests that Fe was mainly leached from basalt. In contrast, the Fe-isotope composition of the sulfides from the study area at the EPR are significantly enriched in light Fe isotopes (average value - 1.63‰), mainly due to the kinetic fractionation during the rapid precipitation process of hydrothermal sulfide. In addition, the pyrite from different hydrothermal fields is enriched in light Fe isotopes, which is consistent with the phenomenon in which light Fe isotopes are preferentially enriched during the precipitation of pyrite. The red oxides have the heaviest Fe-isotope compositions (up to 0.80‰), indicating that heavy Fe isotopes are preferentially enriched in the oxidation product during the late-stage oxidation process. The data obtained from this study and previous studies show a significant difference between the Fe-isotope compositions of the sulfides from the SMAR and EPR. The relatively heavy Fe isotopes compositions of the sulfides from the SMAR may suggest the equilibrium fractionation process under high temperature conditions. The red Fe oxides are enriched in heavy Fe isotopes, indicating that the oxidative weathering processes result in the occurrence of significant Fe-isotope fractionation and the preferential enrichment of heavy Fe isotopes in the oxidation product.

Isotopy of the hydrosphere

NASA Astrophysics Data System (ADS)

Ferronskii, V. I.; Poliakov, V. A.

This book is concerned with the natural relations regarding the distribution of the stable isotopes of hydrogen and oxygen in the hydrosphere, taking into account the most important problems with respect to the dynamics and the origin of waters. The solution of these problems on an isotopic basis is considered. The physicochemical principles of isotope separation are discussed along with the isotopic composition of atmospheric moisture, the isotopic composition of surface continental waters, the hydrogen and oxygen isotopic composition of minerals of magmatic and metamorphic rocks and fluid inclusions, the isotopic composition of groundwaters of modern volcanic regions, and the origin of the earth's hydrosphere in the light of isotopic, cosmochemical, and theoretical studies. Attention is also given to the separation of hydrogen and oxygen isotopes of waters in the underground cycle, the isotopic composition of the deep-formation waters of sedimentary basins, the relationship between surface and ground waters, and the groundwater residence time in an aquifer.

High-precision gamma-ray spectroscopy of 61Cu, an emerging medical isotope used in positron emission tomography

NASA Astrophysics Data System (ADS)

Nelson, N.; Ellison, P.; Nickles, R.; McCutchan, E.; Sonzogni, A.; Smith, S.; Greene, J.; Carpenter, M.; Zhu, S.; Lister, C.; Moran, K.

2017-09-01

61Cu (t1 / 2 = 3.339h) is an important medical isotope used in positron emission tomography (PET) tumor hypoxia imaging scans; however, its beta-plus decay and the subsequent gamma decay of 61Ni has not been studied in over 30 years. Therefore, high quality decay data of 61Cu is desired to determine the overall dose delivered to a patient. In this study, 61Cu was produced at the University of Wisconsin - Madison cyclotron and then assayed using the Gammasphere array at Argonne National Laboratory. Consisting of 70 Compton-suppressed high-purity germanium (HPGe) detectors, Gammasphere provides precise decay data that exceeds that of previous 61Cu studies. γ-ray singles and coincident data were recorded and then analyzed using Radware gf3m software. Through γ- γ coincidence techniques, new γ-ray transitions were identified and high precision determination of γ-ray intensities were made. These modifications and additions to the current decay scheme will be presented, and their impact on the resulting does estimates will be discussed. DOE Isotope Program is acknowledged for funding ST5001030. Work supported by the U.S. DOE under Grant No. DE-FG02-94ER40848 and Contract Nos. DE-AC02-98CH10946 and DE-AC02-06CH11357 and by the Science Undergraduate Laboratory Internship Program (SULI).

Trace Metal Inventories and Lead Isotopic Composition Chronicle a Forest Fire’s Remobilization of Industrial Contaminants Deposited in the Angeles National Forest

PubMed Central

Odigie, Kingsley O.; Flegal, A. Russell

2014-01-01

The amounts of labile trace metals: [Co] (3 to 11 µg g−1), [Cu] (15 to 69 µg g−1), [Ni] (6 to 15 µg g−1), [Pb] (7 to 42 µg g−1), and [Zn] (65 to 500 µg g−1) in ash collected from the 2012 Williams Fire in Los Angeles, California attest to the role of fires in remobilizing industrial metals deposited in forests. These remobilized trace metals may be dispersed by winds, increasing human exposures, and they may be deposited in water bodies, increasing exposures in aquatic ecosystems. Correlations between the concentrations of these trace metals, normalized to Fe, in ash from the fire suggest that Co, Cu, and Ni in most of those samples were predominantly from natural sources, whereas Pb and Zn were enriched in some ash samples. The predominantly anthropogenic source of excess Pb in the ash was further demonstrated by its isotopic ratios (208Pb/207Pb: 206Pb/207Pb) that fell between those of natural Pb and leaded gasoline sold in California during the previous century. These analyses substantiate current human and environmental health concerns with the pyrogenic remobilization of toxic metals, which are compounded by projections of increases in the intensity and frequency of wildfires associated with climate change. PMID:25259524

Study on the mechanical properties of Cu/LDPE composite IUDs.

PubMed

Tang, Ying; Xia, Xianping; Wang, Yun; Xie, Changsheng

2011-03-01

The copper/low-density polyethylene composite (Cu/LDPE composite) intrauterine devices (IUDs), which can eliminate or lessen the side effects of existing IUDs, have been developed in our laboratory. As a novel type of copper-containing IUDs, it is not clear whether the mechanical properties of the Cu/LDPE composite IUDs can meet the need of clinical use or not. Therefore, the mechanical properties of the Cu/LDPE composite IUDs have been studied in the present article. The influence of copper particle content and size on the mechanical properties of the Cu/LDPE composite IUDs was analyzed firstly to provide guidance for the material composition design of the Cu/LDPE composite IUDs, and then the BaSO(4)/LDPE composite, which has been applied as a framework of the existing copper-containing IUDs in clinical use for decades, has been used as reference to judge whether the mechanical properties of the Cu/LDPE composite IUDs can meet the need of clinical use or not. However, the mechanical properties of IUDs cannot be characterized directly. Therefore, the mechanical properties of both the Cu/LDPE composite IUDs and the framework of the existing copper-containing IUDs were investigated by means of tensile test using standard tensile samples, and the fracture surface morphology of the tensile samples was characterized by scanning electron microscopy (SEM). Both the elongation at break and the tensile strength decrease with increasing of copper particle content and increase with increasing of the copper particle size, while the elastic modulus shows an opposite tendency. The tensile strength and elastic modulus of both the Cu/LDPE microcomposite IUDs and the Cu/LDPE nanocomposite IUDs with 25 wt.% of copper particles are higher than those of existing copper-containing IUDs (TCu220C; its framework is made of the BaSO(4)/LDPE composite with 20 wt.% of BaSO(4)). The content and size of the copper particles have significant effect on the mechanical properties of Cu/LDPE composite IUDs. The mechanical properties of both the Cu/LDPE microcomposite IUDs and the Cu/LDPE nanocomposite IUDs with 25 wt.% of copper particles were superior to that of existing copper-containing IUDs, indicating that the novel Cu/LDPE composite IUDs can satisfy the requirement of mechanical properties in clinical application. Copyright © 2011 Elsevier Inc. All rights reserved.

Facile preparation of magnetic mesoporous Fe3O4/C/Cu composites as high performance Fenton-like catalysts

NASA Astrophysics Data System (ADS)

Li, Keyan; Zhao, Yongqin; Janik, Michael J.; Song, Chunshan; Guo, Xinwen

2017-02-01

Fe-Cu composites with different compositions and morphologies were synthesized by a hydrothermal method combined with precursor thermal transformation. γ-Fe2O3/CuO and α-Fe2O3/CuO were obtained by calcining the Fe and Cu tartrates under air atmosphere at 350 °C and 500 °C, respectively, while Fe3O4/C/Cu was obtained by calcining the tartrate precursor under N2 atmosphere at 500 °C. The Fe3O4/C/Cu composite possessed mesoporous structure and large surface area up to 133 m2 g-1. The Fenton catalytic performance of Fe3O4/C/Cu composite was closely related to the Fe/Cu molar ratio, and only proper amounts of Fe and Cu exhibited a synergistic enhancement in Fenton catalytic activity. Cu inclusion reduced Fe3+ to Fe2+, which accelerated the Fe3+/Fe2+ cycles and favored H2O2 decomposition to produce more hydroxyl radicals for methylene blue (MB) oxidation. Due to the photo-reduction of Fe3+ and Cu2+, the Fenton catalytic performance was greatly improved when amending with visible light irradiation in the Fe3O4/C/Cu-H2O2 system, and MB (100 mg L-1) was nearly removed within 60 min. The Fe3O4/C/Cu composite showed good recyclability and could be conveniently separated by an applied magnetic field. Compared with conventional methods for mesoporous composite construction, the thermolysis method using mixed metal tartrates as precursors has the advantages of easy preparation and low cost. This strategy provides a facile, cheap and green method for the synthesis of mesoporous composites as excellent Fenton-like catalysts, without any additional reductants or organic surfactants.

Feasibility of Isotope Harvesting at a Projectile Fragmentation Facility: 67Cu

PubMed Central

Mastren, Tara; Pen, Aranh; Peaslee, Graham F.; Wozniak, Nick; Loveless, Shaun; Essenmacher, Scott; Sobotka, Lee G.; Morrissey, David J.; Lapi, Suzanne E.

2014-01-01

The work presented here describes a proof-of-principle experiment for the chemical extraction of 67Cu from an aqueous beam stop at the National Superconducting Cyclotron Laboratory (NSCL). A 76 MeV/A 67Cu beam was stopped in water, successfully isolated from the aqueous solution through a series of chemical separations involving a chelating disk and anion exchange chromatography, then bound to NOTA-conjugated Herceptin antibodies, and the bound activity was validated using instant thin-layer chromatography (ITLC). The chemical extraction efficiency was found to be 88 ± 3% and the radiochemical yield was ≥95%. These results show that extraction of radioisotopes from an aqueous projectile-fragment beam dump is a feasible method for obtaining radiochemically pure isotopes. PMID:25330839

Mineralogy, geochemistry, and Sr-Pb isotopic geochemistry of hydrothermal massive sulfides from the 15.2°S hydrothermal field, Mid-Atlantic Ridge

NASA Astrophysics Data System (ADS)

Wang, Hao; Li, Xiaohu; Chu, Fengyou; Li, Zhenggang; Wang, Jianqiang; Yu, Xing; Bi, Dongwei

2018-04-01

The 15.2°S hydrothermal field is located at 15.2°S, 13.4°W within the Mid-Atlantic Ridge (MAR) and was initially discovered during Cruise DY125-22 by the Chinese expedition during R/V Dayangyihao in 2011. Here, we provide detailed mineralogical, bulk geochemical, and Sr-Pb isotopic data for massive sulfides and basalts from the 15.2°S hydrothermal field to improve our understanding of the mineral compositions, geochemical characteristics, type of hydrothermal field, and the source of metals present at this vent site. The samples include 14 massive sulfides and a single basalt. The massive sulfides are dominated by pyrite with minor amounts of sphalerite and chalcopyrite, although a few samples also contain minor amounts of gordaite, a sulfate mineral. The sulfides have bulk compositions that contain low concentrations of Cu + Zn (mean 7.84 wt%), Co (mean 183 ppm), Ni (mean 3 ppm), and Ba (mean 16 ppm), similar to the Normal Mid-Ocean Ridge Basalt (N-MORB) type deposits along the MAR but different to the compositions of the Enriched-MORB (E-MORB) and ultramafic type deposits along this spreading ridge. Sulfides from the study area have Pb isotopic compositions (206Pb/204Pb = 18.4502-18.4538, 207Pb/204Pb = 15.4903-15.4936, 208Pb/204Pb = 37.8936-37.9176) that are similar to those of the basalt sample (206Pb/204Pb = 18.3381, 207Pb/204Pb = 15.5041, 208Pb/204Pb = 37.9411), indicating that the metals within the sulfides were derived from leaching of the surrounding basaltic rocks. The sulfides also have 87Sr/86Sr ratios (0.708200-0.709049) that are much higher than typical MAR hydrothermal fluids (0.7028-0.7046), suggesting that the hydrothermal fluids mixed with a significant amount of seawater during massive sulfide precipitation.

Tracing dust transport from Middle-East over Delhi in March 2012 using metal and lead isotope composition

NASA Astrophysics Data System (ADS)

Kumar, S.; Aggarwal, S. G.; Malherbe, J.; Barre, J. P. G.; Berail, S.; Gupta, P. K.; Donard, O. F. X.

2016-05-01

A severe dust-storm which was originated in Middle-East crossed over Delhi during March 20-22, 2012. We have collected these dust-storm (DS) aerosol samples, and analyzed them for selected metals (As, Cd, Cr, Cu, Fe, Ni, Pb, Sb, Se, Sn, Sr, V and Zn) together with after dust-storm (ADS) and winter (WS) samples. High aerosol mass loadings were observed in DS samples (1097-1965 μg/m3). On the contrary, metals derived prominently from the anthropogenic sources were found lower in concentration compared to that of ADS and WS aerosols. We observed significantly high concentrations of Ni and V (which are abundantly found in crude oils of Middle-East origin) in the DS samples than that of ADS and WS samples. Also enrichment factor (EF) of these metals with respect to Fe shows no significant enrichment (<10). Fe (and Sr) concentrations were also 3-5 fold higher in DS samples compared to ADS and WS. These results suggest that Ni and V can be used as tracers for dust aerosols transported from Middle-East region. Lead isotope signatures can tell about the variation in the sources of urban aerosols. Therefore Pb isotope analyses of these samples were performed using MC-ICP-MS. The isotope ratios, 208Pb/206Pb is determined to be (mean ± sd) 2.1315 ± 0.0018, 2.1370 ± 0.0022 and 2.1389 ± 0.0016, whereas 206Pb/207Pb is 1.1311 ± 0.0022, 1.1244 ± 0.0017 and 1.1233 ± 0.0016 in DS, ADS and WS aerosols, respectively. There is a clear distinction in Pb isotope composition between DS and urban (ADS and WS) aerosols. Further, these results suggest that in urban aerosols, Pb is less radiogenic in nature compared to that of in transported dust aerosols collected in New Delhi.

Zinc and sulfur isotope variation in sphalerite from carbonate-hosted zinc deposits, Cantabria, Spain

NASA Astrophysics Data System (ADS)

Pašava, Jan; Tornos, Fernando; Chrastný, Vladislav

2014-10-01

We studied zinc and sulfur isotopes and the chemical composition of sphalerite samples from Picos de Europa (Aliva mine) and sphalerite and hydrozincite samples from La Florida mine, two carbonate-hosted Mississippi Valley-type (MVT) deposits located in northern Spain; despite being close, they are hosted in carbonatic rocks of different ages, Lower Carboniferous and Lower Cretaceous, respectively. The two generations of sphalerite at Picos de Europa show different δ66Zn values (stage 1 sphalerite +0.24 per mil and stage 2 sphalerite from -0.75 to +0.08 per mil). Both generations also differ in the sulfur isotope composition (stage 1 has δ34S = +6.6 and stage 2 has δ34S = -0.9 to +2.9 per mil) and the chemical composition (stage 1 sphalerite, compared to stage 2 sphalerite, is significantly enriched in Pb, As, Mn, Sb, slightly enriched in Ag, Ni, and Cu and depleted in Co, Ga, Tl, Te, Ge, and Sn). We suggest that Zn isotope fractionation was controlled predominantly by pH and T changes. High Zn isotope values reflect rapid precipitation of sphalerite from higher-temperature acidic fluids that carried Zn mostly as chloride species after interaction with carbonate rocks while lower Zn isotope values most likely resulted from a longer precipitation process from fluid at higher pH and decreasing T that carried dominantly Zn sulfide species. At La Florida, sphalerite samples show light 66Zn-depleted signatures with δ66Zn values from -0.80 to -0.01 per mil (mostly between -0.80 and -0.24 per mil) and δ34S values from +10.7 to +15.7 per mil without any relationship between the δ66Zn and δ34S values. Here, the variation in Zn isotope values is interpreted as related to mixing of fluids from two reservoirs. The Zn was carried by a single deep-seated and higher T (~250-320 °C) fluid, and precipitation took place after mixing with a connate S-rich fluid in a system with mH2S > mZn2+ as a result of change in pH, T, and Zn predominant species. The light δ66Zn accompanied by heavy δ34S values resulted from fractionation of Zn aqueous sulfides at near-neutral pH and decreasing T. Hydrozincite samples show much heavier δ66Zn values (+0.21 to +0.33 per mil), consistent with fractionation during supergene processes.

Variations in Urine Calcium Isotope: Composition Reflect Changes in Bone Mineral Balance in Humans

NASA Technical Reports Server (NTRS)

Skulan, Joseph; Anbar, Ariel; Bullen, Thomas; Puzas, J. Edward; Shackelford, Linda; Smith, Scott M.

2004-01-01

Changes in bone mineral balance cause rapid and systematic changes in the calcium isotope composition of human urine. Urine from subjects in a 17 week bed rest study was analyzed for calcium isotopic composition. Comparison of isotopic data with measurements of bone mineral density and metabolic markers of bone metabolism indicates the calcium isotope composition of urine reflects changes in bone mineral balance. Urine calcium isotope composition probably is affected by both bone metabolism and renal processes. Calcium isotope. analysis of urine and other tissues may provide information on bone mineral balance that is in important respects better than that available from other techniques, and illustrates the usefulness of applying geochemical techniques to biomedical problems.

Tungsten fiber reinforced copper matrix composites: A review

NASA Technical Reports Server (NTRS)

Mcdanels, David L.

1989-01-01

Tungsten fiber reinforced copper matrix (W/Cu) composites have served as an ideal model system with which to analyze the properties of metal matrix composites. A series of research programs were conducted to investigate the stress-strain behavior of W/Cu composites; the effect of fiber content on the strength, modulus, and conductivity of W/Cu composites; and the effect of alloying elements on the behavior of tungsten wire and of W/Cu composites. Later programs investigated the stress-rupture, creep, and impact behavior of these composites at elevated temperatures. Analysis of the results of these programs as allows prediction of the effects of fiber properties, matrix properties, and fiber content on the properties of W/Cu composites. These analyses form the basis for the rule-of-mixtures prediction of composite properties which was universally adopted as the criteria for measuring composite efficiency. In addition, the analyses allows extrapolation of potential properties of other metal matrix composites and are used to select candidate fibers and matrices for development of tungsten fiber reinforced superalloy composite materials for high temperature aircraft and rocket engine turbine applications. The W/Cu composite efforts are summarized, some of the results obtained are described, and an update is provided on more recent work using W/Cu composites as high strength, high thermal conductivity composite materials for high heat flux, elevated temperature applications.

Copper-arsenic decoupling in an active geothermal system: A link between pyrite and fluid composition

NASA Astrophysics Data System (ADS)

Tardani, Daniele; Reich, Martin; Deditius, Artur P.; Chryssoulis, Stephen; Sánchez-Alfaro, Pablo; Wrage, Jackie; Roberts, Malcolm P.

2017-05-01

Over the past few decades several studies have reported that pyrite hosts appreciable amounts of trace elements which commonly occur forming complex zoning patterns within a single mineral grain. These chemical zonations in pyrite have been recognized in a variety of hydrothermal ore deposit types (e.g., porphyry Cu-Mo-Au, epithermal Au deposits, iron oxide-copper-gold, Carlin-type and Archean lode Au deposits, among others), showing, in some cases, marked oscillatory alternation of metals and metalloids in pyrite growth zones (e.g., of Cu-rich, As-(Au, Ag)-depleted zones and As-(Au, Ag)-rich, Cu-depleted zones). This decoupled geochemical behavior of Cu and As has been interpreted as a result of chemical changes in ore-forming fluids, although direct evidence connecting fluctuations in hydrothermal fluid composition with metal partitioning into pyrite growth zones is still lacking. In this study, we report a comprehensive trace element database of pyrite from the Tolhuaca Geothermal System (TGS) in southern Chile, a young and active hydrothermal system where fewer pyrite growth rims and mineralization events are present and the reservoir fluid (i.e. ore-forming fluid) is accessible. We combined the high-spatial resolution and X-ray mapping capabilities of electron microprobe analysis (EMPA) with low detection limits and depth-profiling capacity of secondary-ion mass spectrometry (SIMS) in a suite of pyrite samples retrieved from a ∼1 km drill hole that crosses the argillic (20-450 m) and propylitic (650-1000 m) alteration zones of the geothermal system. We show that the concentrations of precious metals (e.g., Au, Ag), metalloids (e.g., As, Sb, Se, Te), and base and heavy metals (e.g., Cu, Co, Ni, Pb) in pyrite at the TGS are significant. Among the elements analyzed, As and Cu are the most abundant with concentrations that vary from sub-ppm levels to a few wt.% (i.e., up to ∼5 wt.% As, ∼1.5 wt.% Cu). Detailed wavelength-dispersive spectrometry (WDS) X-ray maps and SIMS depth vs. isotope concentration profiles reveal that pyrites from the TGS are characterized by chemical zoning where the studied elements occur in different mineralogical forms. Arsenic and Co occur as structurally bound elements in pyrite, Cu and Au in pyrite can occur as both solid solution and submicron-sized particles of chalcopyrite and native Au (or Au tellurides), respectively. Pyrites from the deeper propylitic zone do not show significant zonation and high Cu-(Co)-As concentrations correlate with each other. In contrast, well-developed zonations were detected in pyrite from the shallow argillic alteration zone, where Cu(Co)-rich, As-depleted cores alternate with Cu(Co)-depleted, As-rich rims. These microanalytical data were contrasted with chemical data of fluid inclusions in quartz and calcite veins (high Cu/As ratios) and borehole fluid (low Cu/As ratios) reported at the TGS, showing a clear correspondence between Cu and As concentrations in pyrite-forming fluids and chemical zonation in pyrite. These observations provide direct evidence supporting the selective partitioning of metals into pyrite as a result of changes in ore-forming fluid composition, most likely due to separation of a single-phase fluid into a low-density vapor and a denser brine, capable of fractionating Cu and As.

Preparation and cupric ion release behavior of Cu/LDPE porous composites with tunable pore morphology for intrauterine devices.

PubMed

Xiao, Lian; Xia, Xianping; Xie, Changsheng; Ge, Man; Xiao, Cheng; Cai, Shuizhou

2013-07-01

Copper/low-density polyethylene (Cu/LDPE) porous composites are novel materials for copper-containing intrauterine devices (Cu-IUDs). Here we report a method, i.e., by changing the mass ratio of two kinds of porogens that have different melting points through the combined techniques of injection molding and particulate leaching, to prepare the Cu/LDPE porous composites with tunable pore morphology. After these Cu/LDPE porous composites with different pore morphologies were obtained, the influences of pore morphologies on their cupric ion release behaviors were studied. The results show that the pore morphology has great influence on the cupric ion release behavior of Cu/LDPE porous composites. This phenomenon is caused by the different influences of different pore morphologies on the effective porosity and the surface hydrophilicity. And those results can be applied to guide the fabrication of Cu/LDPE porous composite Cu-IUDs with minimal weight at an appropriate cupric ion release rate. Copyright © 2013 Elsevier B.V. All rights reserved.

Interface structure and properties of CNTs/Cu composites fabricated by electroless deposition and spark plasma sintering

NASA Astrophysics Data System (ADS)

Wang, Hu; Zhang, Zhao-Hui; Hu, Zheng-Yang; Song, Qi; Yin, Shi-Pan

2018-01-01

In this paper, we fabricated a novel copper matrix composites reinforced by carbon nanotubes (CNTs) using electroless deposition (ED) and spark plasma sintering technique. Microstructure, mechanical, electric conductivity, and thermal properties of the CNTs/Cu composites were investigated. The results show that a favorable interface containing C-O and O-Cu bond was formed between CNTs and matrix when the CNTs were coated with nano-Cu by ED method. Thus, we accomplished the uniformly dispersed CNTs in the CNTs/Cu powders and compacted composites, which eventually leads to the enhancement of the mechanical properties of the CNTs/Cu composites in the macro-scale environment. However, the interface structure can hinder the movement of carriers and free electrons and increase the interface thermal resistance, which leads to modest decrease of electrical and thermal conductivity of the CNTs/Cu composites.

Asian dust input in the western Philippine Sea: Evidence from radiogenic Sr and Nd isotopes

NASA Astrophysics Data System (ADS)

Jiang, Fuqing; Frank, Martin; Li, Tiegang; Chen, Tian-Yu; Xu, Zhaokai; Li, Anchun

2013-05-01

The radiogenic strontium (Sr) and neodymium (Nd) isotope compositions of the detrital fraction of surface and subsurface sediments have been determined to trace sediment provenance and contributions from Asian dust off the east coast of Luzon Islands in the western Philippine Sea. The Sr and Nd isotope compositions have been very homogenous near the east coast of the Luzon Islands during the latest Quaternary yielding relatively least radiogenic Sr (87Sr/86Sr = 0.70453 to 0.70491) and more radiogenic Nd isotope compositions (ɛNd(0) = +5.3 to +5.5). These isotope compositions are similar to Luzon rocks and show that these sediments were mainly derived from the Luzon Islands. In contrast, the Sr and Nd isotope compositions of sediments on the Benham Rise and in the Philippine Basin are markedly different in that they are characterized by overall more variable and more radiogenic Sr isotope compositions (87Sr/86Sr = 0.70452 to 0.70723) and less radiogenic Nd isotope compositions (ɛNd(0) = -5.3 to +2.4). The Sr isotope composition in the Huatung Basin is intermediate between those of the east coast of Luzon and Benham Rise, but shows the least radiogenic Nd isotope compositions. The data are consistent with a two end-member mixing relationship between Luzon volcanic rocks and eolian dust from the Asian continent, which is characterized by highly radiogenic Sr and unradiogenic Nd isotope compositions. The results show that Asian continental dust contributes about 10-50% of the detrital fraction of the sediments on Benham Rise in the western Philippine Sea, which offers the potentials to reconstruct the climatic evolution of eastern Asia from these sediments and compare this information to the records from the central and northern Pacific.

Development of Cu Reinforced SiC Particulate Composites

NASA Astrophysics Data System (ADS)

Singh, Harshpreet; Kumar, Lailesh; Nasimul Alam, Syed

2015-02-01

This paper presents the results of Cu-SiCp composites developed by powder metallurgy route and an attempt has been made to make a comparison between the composites developed by using unmilled Cu powder and milled Cu powder. SiC particles as reinforcement was blended with unmilled and as-milled Cu powderwith reinforcement contents of 10, 20, 30, 40 vol. % by powder metallurgy route. The mechanical properties of pure Cu and the composites developed were studied after sintering at 900°C for 1 h. Density of the sintered composites were found out based on the Archimedes' principle. X-ray diffraction of all the composites was done in order to determine the various phases in the composites. Scanning electron microscopy (SEM) and EDS (electron diffraction x-ray spectroscopy) was carried out for the microstructural analysis of the composites. Vickers microhardness tester was used to find out the hardness of the samples. Wear properties of the developed composites were also studied.

Evaluation of metals and hydrocarbons in sediments from a tropical tidal flat estuary of Southern Brazil.

PubMed

Costa, Eduardo S; Grilo, Caroline F; Wolff, George A; Thompson, Anu; Figueira, Rubens Cesar Lopes; Neto, Renato Rodrigues

2015-03-15

Although the Passagem Channel estuary, Espírito Santo State, Brazil, is located in an urbanized and industrialized region, it has a large mangrove system. Here we examined natural and anthropogenic inputs that may influence trace metal (Cd, Cr, Cu, Ni, Sc, Pb and Zn) and hydrocarbon (n-alkane and terpane) deposition in three sediment cores collected in the tidal flat zone of the estuary. The cores were also analyzed for carbonate, grain size and stable isotopic composition (δ(13)Corg. and δ(15)Ntotal). Metal enrichment and its association to petroleum hydrocarbons in the surficial sediments of one of the cores, indicate crude oil and derivative inputs, possibly from small vessels and road run-off from local heavy automobile traffic. At the landward sites, the major contributions for metals and hydrocarbons are from natural sources, but in one case, Cu may have been enriched by domestic effluent inputs. Copyright © 2014 Elsevier Ltd. All rights reserved.

Sulfur Isotope Composition of Putative Primary Troilite in Chondrules

NASA Technical Reports Server (NTRS)

Tachibana, Shogo; Huss, Gary R.

2002-01-01

Sulfur isotope compositions of putative primary troilites in chondrules from Bishunpur were measured by ion probe. These primary troilites have the same S isotope compositions as matrix troilites and thus appear to be isotopically unfractionated. Additional information is contained in the original extended abstract.

Non-linear dynamics of stable carbon and hydrogen isotope signatures based on a biological kinetic model of aerobic enzymatic methane oxidation.

PubMed

Vavilin, Vasily A; Rytov, Sergey V; Shim, Natalia; Vogt, Carsten

2016-06-01

The non-linear dynamics of stable carbon and hydrogen isotope signatures during methane oxidation by the methanotrophic bacteria Methylosinus sporium strain 5 (NCIMB 11126) and Methylocaldum gracile strain 14 L (NCIMB 11912) under copper-rich (8.9 µM Cu(2+)), copper-limited (0.3 µM Cu(2+)) or copper-regular (1.1 µM Cu(2+)) conditions has been described mathematically. The model was calibrated by experimental data of methane quantities and carbon and hydrogen isotope signatures of methane measured previously in laboratory microcosms reported by Feisthauer et al. [ 1 ] M. gracile initially oxidizes methane by a particulate methane monooxygenase and assimilates formaldehyde via the ribulose monophosphate pathway, whereas M. sporium expresses a soluble methane monooxygenase under copper-limited conditions and uses the serine pathway for carbon assimilation. The model shows that during methane solubilization dominant carbon and hydrogen isotope fractionation occurs. An increase of biomass due to growth of methanotrophs causes an increase of particulate or soluble monooxygenase that, in turn, decreases soluble methane concentration intensifying methane solubilization. The specific maximum rate of methane oxidation υm was proved to be equal to 4.0 and 1.3 mM mM(-1) h(-1) for M. sporium under copper-rich and copper-limited conditions, respectively, and 0.5 mM mM(-1) h(-1) for M. gracile. The model shows that methane oxidation cannot be described by traditional first-order kinetics. The kinetic isotope fractionation ceases when methane concentrations decrease close to the threshold value. Applicability of the non-linear model was confirmed by dynamics of carbon isotope signature for carbon dioxide that was depleted and later enriched in (13)C. Contrasting to the common Rayleigh linear graph, the dynamic curves allow identifying inappropriate isotope data due to inaccurate substrate concentration analyses. The non-linear model pretty adequately described experimental data presented in the two-dimensional plot of hydrogen versus carbon stable isotope signatures.

Cu2S-Cu-TiO2 mesoporous carbon composites for the degradation of high concentration of methyl orange under visible light

NASA Astrophysics Data System (ADS)

Zhang, Liang; Zhao, Yuan; Zhong, Lvling; Wang, Yang; Chai, Shouning; Yang, Tao; Han, Xuanli

2017-11-01

A Schiff base compound was used to prepare a Cu2S-Cu-TiO2 mesoporous carbon composite photocatalyst (Cu2S-Cu-TiO2/MC) by a simple precipitation-carbonization method with a carbonization temperature of 750 °C. X-ray diffraction and x-ray photoelectron spectroscopy studies show that Cu2S, Cu, and TiO2 exist in Cu2S-Cu-TiO2/MC in the form of nanometer-sized particles. Scanning electron microscope and transmission electron microscope images show that the composites form a spherical carbon structure inlaid with Cu2S and Cu and coated TiO2. The Brunauer-Emmett-Teller test shows that the material has a large specific surface area (76.14 m2/g) and mesoporous structure. UV-vis diffuse reflection spectroscopy and photoluminescence spectroscopy indicate that the recombination of photo-generated electrons and holes in the samples were inhibited. The composites show good degradation performance in a high concentration (300 mg/L) of methyl orange (MO) solution under visible light. The composites exhibit great potential in the treatment of dyes for wastewater treatment.

Copper absorption from foods labelled intrinsically and extrinsically with Cu-65 stable isotope.

PubMed

Harvey, L J; Dainty, J R; Beattie, J H; Majsak-Newman, G; Wharf, S G; Reid, M D; Fairweather-Tait, S J

2005-03-01

To determine copper absorption from copper containing foods labelled either intrinsically or extrinsically with a highly enriched Cu-65 stable isotope label. A longitudinal cross-over study. The study was conducted at the Institute of Food Research, Human Nutrition Unit, Norwich, UK. Subjects were recruited locally via advertisements placed around the Norwich Research Park. A total of 10 volunteers (nine female, one male) took part in the study, but not all volunteers completed each of the test meals. A highly enriched Cu-65 stable isotope label was administered to volunteers in the form of a reference dose or in breakfast test meals consisting of red wine, soya beans, mushrooms or sunflower seeds. Faecal monitoring and mass spectrometry techniques were used to estimate the relative quantities of copper absorbed from the different test meals. True copper absorption from the reference dose (54%) was similar to extrinsically labelled red wine (49%) and intrinsically labelled sunflower seeds (52%), but significantly higher than extrinsically labelled mushrooms (35%), intrinsically (29%) and extrinsically (15%) labelled soya beans and extrinsically labelled sunflower seed (32%) test meals. The use of Cu-65 extrinsic labels in copper absorption studies requires validation according to the food being examined; intrinsic and extrinsic labelling produced significantly different results for sunflower seeds.

New geologic, fluid inclusion and stable isotope studies on the controversial Igarapé Bahia Cu-Au deposit, Carajás Province, Brazil

NASA Astrophysics Data System (ADS)

Dreher, Ana M.; Xavier, Roberto P.; Taylor, Bruce E.; Martini, Sérgio L.

2008-02-01

The Igarapé Bahia Cu-Au deposit in the Carajás Province, Brazil, is hosted by steeply dipping metavolcano-sedimentary rocks of the Igarapé Bahia Group. This group consists of a low greenschist grade unit of the Archean (˜2,750 Ma) Itacaiúnas Supergroup, in which other important Cu-Au and iron ore deposits of the Carajás region are also hosted. The orebody at Igarapé Bahia is a fragmental rock unit situated between chloritized basalt, with associated hyaloclastite, banded iron formation (BIF), and chert in the footwall and mainly coarse- to fine-grained turbidites in the hanging wall. The fragmental rock unit is a nearly concordant, 2 km long and 30-250 m thick orebody made up of heterolithic, usually matrix-supported rocks composed mainly of coarse basalt, BIF, and chert clasts derived from the footwall unit. Mineralization is confined to the fine-grained matrix and comprises disseminated to massive chalcopyrite accompanied by magnetite, gold, U- and light rare earth element (LREE)-minerals, and minor other sulfides like bornite, molybdenite, cobaltite, digenite, and pyrite. Gangue minerals include siderite, chlorite, amphibole, tourmaline, quartz, stilpnomelane, epidote, and apatite. A less important mineralization style at Igarapé Bahia is represented by late quartz-chalcopyrite-calcite veins that crosscut all rocks in the deposit area. Fluid inclusions trapped in a quartz cavity in the ore unit indicate that saline aqueous fluids (5 to 45 wt% NaCl + CaCl2 equiv), together with carbonic (CO2 ± CH4) and low-salinity aqueous carbonic (6 wt% NaCl equiv) fluids, were involved in the mineralization process. Carbonates from the fragmental layer have δ13C values from -6.7 to -13.4 per mil that indicate their origin from organic and possibly also from magmatic carbon. The δ34S values for chalcopyrite range from -1.1 to 5.6 per mil with an outlier at -10.8 per mil, implying that most sulfur is magmatic or leached from magmatic rocks, whereas a limited contribution of reduced and oxydized sulfur is also evident. Oxygen isotopic ratios in magnetite, quartz, and siderite yield calculated temperatures of ˜400°C and δ18O-enriched compositions (5 to 16.5 per mil) for the ore-forming fluids that suggest a magmatic input and/or an interaction with 18O-rich, probably sedimentary rocks. The late veins of the Igarapé Bahia deposit area were formed from saline aqueous fluids (2 to 60 wt% NaCl + CaCl2 equiv) with δ18Ofluid compositions around 0 per mil that indicate contribution from meteoric fluids. With respect to geological features, Igarapé Bahia bears similarity with syngenetic, volcanic-hosted massive sulfide (VHMS)-type deposits, as indicated by the volcano-sedimentary geological context, stratabound character, and association with submarine volcanic flows, hyaloclastite, and exhalative beds such as BIF and chert. On the other hand, the highly saline ore fluids and the mineral assemblage, dominated by magnetite and chalcopyrite, with associated gold, U- and LREE-minerals and scarce pyrite, indicate that Igarapé Bahia belongs to the Fe oxide Cu-Au (IOCG) group of deposits. The available geochronologic data used to attest syngenetic or epigenetic origins for the mineralization are either imprecise or may not represent the main mineralization episode but a later, superimposed event. The C, S, and O isotopic results obtained in this study do not clearly discriminate between fluid sources. However, recent B isotope data obtained on tourmaline from the matrix of the fragmental rock ore unit (Xavier, Wiedenbeck, Dreher, Rhede, Monteiro, Araújo, Chemical and boron isotopic composition of tourmaline from Archean and Paleoproterozoic Cu-Au deposits in the Carajás Mineral Province, 1° Simpósio Brasileiro de Metalogenia, Gramado, Brazil, extended abstracts, CD-ROM, 2005) provide strong evidence of the involvement of a marine evaporitic source in the hydrothermal system of Igarapé Bahia. Evaporite-derived fluids may explain the high salinities and the low reduced sulfur mineral paragenesis observed in the deposit. Evaporite-derived fluids also exclude a significant participation of magmatic or mantle-derived fluids, reinforcing the role of nonmagmatic brines in the genesis of Igarapé Bahia. Considering this aspect and the geological features, the possibility that the deposit was generated by a hydrothermal submarine system whose elevated salinity was acquired by leaching of ancient evaporite beds should be evaluated.

Fabrication and surface enhanced Raman scattering effect of centimeter level AgCuAu composite nanowires

NASA Astrophysics Data System (ADS)

Xu, Dapeng; Zhang, Song; Yang, Wei; Chen, Jian

2017-10-01

Centimeter level AgCuAu composite nanowires were prepared by a solid-state ionics method under a direct current electric field (DCEF) using fast ionic conductor RbAg4I5 films and vacuum thermal evaporation method. The surface morphology and chemical composition of the AuAgCu composite nanowires were characterized by scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS), respectively. Raman enhancement performance of the AgCuAu composite nanowires substrates was detected by Rhodamine 6G (R6G) aqueous solutions as probe molecules. Long-range order and short-range order AgCuAu composite nanowires with the length of 1 cm were prepared. The nanowires were bamboo-shaped with high surface roughness and the diameters of nanowires ranged from 60 to 100 nm. The molar ratio of Ag:Cu:Au in composite nanowires is 15:2:1. The intrinsic Raman peaks of 10-16 mol/L R6G at 612, 773, 1125, 1182, 1307, 1361, 1418, 1506, 1545, 1575, 1597, 1650 cm-1 are all present when AgCuAu composite nanowires were used as the SERS substrates.

Magmatic controls on the genesis of porphyry Cu-Mo-Au deposits: The Bingham Canyon example

NASA Astrophysics Data System (ADS)

Grondahl, Carter; Zajacz, Zoltán

2017-12-01

Bingham Canyon is one of the world's largest porphyry Cu-Mo-Au deposits and was previously used as an example to emphasize the role of magma mixing and magmatic sulphide saturation in the enhancement of ore fertility of magmatic systems. We analyzed whole rocks, minerals, and silicate melt inclusions (SMI) from the co-genetic, ore-contemporaneous volcanic package (∼38 Ma). As opposed to previous propositions, whole-rock trace element signatures preclude shoshonite-latite genesis via mixing of melanephelinite and trachyte or rhyolite, whereas core to rim compositional profiles of large clinopyroxene phenocrysts suggests the amalgamation of the ore-related magma reservoir by episodic recharge of shoshonitic to latitic magmas with various degrees of differentiation. Major and trace element and Sr and Nd isotopic signatures indicate that the ore-related shoshonite-latite series were generated by low-degree partial melting of an ancient metasomatized mantle source yielding volatile and ore metal rich magmas. Latite and SMI compositions can be reproduced by MELTS modeling assuming 2-step lower and upper crustal fractionation of a primary shoshonite with minimal country rock assimilation. High oxygen fugacities (≈ NNO + 1) are prevalent as evidenced by olivine-spinel oxybarometry, high SO3 in apatite, and anhydrite saturation. The magma could therefore carry significantly more S than would have been possible at more reducing conditions, and the extent of ore metal sequestration by magmatic sulphide saturation was minimal. The SMI data show that the latites were Cu rich, with Cu concentrations in the silicate melt reaching up to 300-400 ppm at about 60 wt% SiO2. The Au and Ag concentrations are also high (1.5-4 and 50-200 ppb, respectively), but show less variation with SiO2. A sudden drop in Cu and S concentrations in the silicate melt at around 65 wt% SiO2 in the presence of high Cl, Mo, Ag, and Au shows that the onset of effective metal extraction by fluid exsolution occurred at a relatively late stage of magma evolution. Overall, our results show that fluid exsolution during simple magmatic differentiation of oxidized alkaline magmas is capable of producing giant porphyry Cu deposits.

Chlorine isotope fractionation during supergene enrichment of copper

NASA Astrophysics Data System (ADS)

Reich, M.; Barnes, J.; Barra, F.; Milojevic, C.; Drew, D.

2017-12-01

Supergene enrichment of Cu deposits in the Atacama Desert has played a critical role in making this the prime Cu-producing province of the world. The Cu-hydroxychloride atacamite is a major component of supergene zones in this region whereas in similar deposits elsewhere it is rare. Atacamite requires saline water to form and dissolves rapidly when exposed to fresh, meteoric water. Previous chlorine stable isotope data [1] for atacamite mineralization at the Radomiro Tomic, Chuquicamata and Mina Sur Cu deposits show δ37Cl values that range from -0.1 to +0.2‰, indicating a similar nonmagmatic source for the introduction of chloride. However, distal atacamite mineralization on the periphery of these orebodies show more fractionated and lighter δ37Cl values (-3.2 to -0.1‰). Although little disagreement currently exists about the involvement of saline groundwater during the formation of atacamite [2], no δ37Cl data are currently available for atacamite within a single deposit and/or supergene enrichment profile that allow explaining the aforementioned differences in the observed δ37Cl values. Furthermore, no experimental data for chlorine isotope fractionation between Cu-hydroxychloride minerals and water exist that help evaluate possible mechanisms of fractionation along the groundwater flow path. Here we present a new database that combines detailed mineralogical observations with δ37Cl data of atacamite along a thick ( 100 m) supergene enrichment profile at the Barreal Seco IOCG deposit in the Atacama Desert of northern Chile. Chlorine stable isotope data of atacamite vary between -0.62 and +2.1 ‰ and show a well-defined trend where δ37Cl values progressively decrease (become lighter) with depth. These data, when combined with new experimental determinations of chlorine isotope fractionation between atacamite and water, point to changes triggered by the progressive deepening of groundwater tables during Andean uplift and the extreme desiccation of Atacama. References [1] Arcuri T, Brimhall G (2003) The chloride source for atacamite mineralization at the Radomiro Tomic porphyry copper deposit, Northern Chile. Econ Geol 98:1667-1681 [2] Reich M et al. (2009) Supergene enrichment of copper deposits since the onset of modern hyperaridity in the Atacama Desert, Chile. Miner Deposita 44: 497-504

Atomic Weights and Isotopic Compositions

National Institute of Standards and Technology Data Gateway

SRD 144 Atomic Weights and Isotopic Compositions (Web, free access)   The atomic weights are available for elements 1 through 111, and isotopic compositions or abundances are given when appropriate.

Magnesium isotopic composition of the Earth and chondrites

NASA Astrophysics Data System (ADS)

Teng, Fang-Zhen; Li, Wang-Ye; Ke, Shan; Marty, Bernard; Dauphas, Nicolas; Huang, Shichun; Wu, Fu-Yuan; Pourmand, Ali

2010-07-01

To constrain further the Mg isotopic composition of the Earth and chondrites, and investigate the behavior of Mg isotopes during planetary formation and magmatic processes, we report high-precision (±0.06‰ on δ 25Mg and ±0.07‰ on δ 26Mg, 2SD) analyses of Mg isotopes for (1) 47 mid-ocean ridge basalts covering global major ridge segments and spanning a broad range in latitudes, geochemical and radiogenic isotopic compositions; (2) 63 ocean island basalts from Hawaii (Kilauea, Koolau and Loihi) and French Polynesia (Society Island and Cook-Austral chain); (3) 29 peridotite xenoliths from Australia, China, France, Tanzania and USA; and (4) 38 carbonaceous, ordinary and enstatite chondrites including 9 chondrite groups (CI, CM, CO, CV, L, LL, H, EH and EL). Oceanic basalts and peridotite xenoliths have similar Mg isotopic compositions, with average values of δ 25Mg = -0.13 ± 0.05 (2SD) and δ 26Mg = -0.26 ± 0.07 (2SD) for global oceanic basalts ( n = 110) and δ 25Mg = -0.13 ± 0.03 (2SD) and δ 26Mg = -0.25 ± 0.04 (2SD) for global peridotite xenoliths ( n = 29). The identical Mg isotopic compositions in oceanic basalts and peridotites suggest that equilibrium Mg isotope fractionation during partial melting of peridotite mantle and magmatic differentiation of basaltic magma is negligible. Thirty-eight chondrites have indistinguishable Mg isotopic compositions, with δ 25Mg = -0.15 ± 0.04 (2SD) and δ 26Mg = -0.28 ± 0.06 (2SD). The constancy of Mg isotopic compositions in all major types of chondrites suggest that primary and secondary processes that affected the chemical and oxygen isotopic compositions of chondrites did not significantly fractionate Mg isotopes. Collectively, the Mg isotopic composition of the Earth's mantle, based on oceanic basalts and peridotites, is estimated to be -0.13 ± 0.04 for δ 25Mg and -0.25 ± 0.07 for δ 26Mg (2SD, n = 139). The Mg isotopic composition of the Earth, as represented by the mantle, is similar to chondrites. The chondritic composition of the Earth implies that Mg isotopes were well mixed during accretion of the inner solar system.

Characterization Of Nuclear Materials Using Time-Of-Flight ICP-MS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buerger, Stefan; Riciputi, Lee R; Bostick, Debra A

2006-01-01

The investigation of illicit trafficking of nuclear materials, nuclear safeguards analysis, and non-proliferation control requires sensitive and isotope-selective detection methods to gain crucial nuclear forensic information like isotope 'fingerprints' and multi-element signatures. The advantage of time-of-flight (TOF) mass spectrometry - quasi-simultaneous multi-mass analysis - combined with an inductively coupled plasma (ICP) ion source provides an analytical instrument with multi-element and multi-isotope capability and good detection limits. A TOF-ICP-MS system thus appears to be an advantageous choice for the investigation and characterization of nuclear materials. We present here results using a GBC OptiMass 8000 time-of-flight ICP-MS for the isotope screening ofmore » solid samples by laser ablation and the multi-element determination of impurities in uranium ore concentrates using matrix matched standards. A laser ablation system (New Wave Research, UP 213) coupled to the TOF-ICP-MS instrument has been used to optimize the system for analysis of non-radioactive metal samples of natural isotopic composition for a variety of elements including Cu, Sr, Zr, Mo, Cd, In, Ba, Ta, W, Re, Pt, and Pb in pure metals, alloys, and glasses to explore precision, accuracy, and detection limits. Similar methods were then applied to measure uranium. When the laser system is optimized, no mass bias correction is required. Precision and accuracy for the determination of the isotopic composition is typically 1 - 3% for elemental concentrations of as little as 50 ppm in the matrix, with no requirement for sample preparation. The laser ablation precision and accuracy are within ~10x of the instrumental limits for liquid analysis (0.1%). We have investigated the capabilities of the TOF-ICP-MS for the analysis of impurities in uranium matrices. Matrix matching has been used to develop calibration curves for a range of impurities (alkaline, earth-alkaline, transition metals, and rare earth elements). These calibration curves have been used to measure impurities in a number of uranium samples. The results from the TOF-ICP-MS will be compared with other mass spectrometric methods.« less

Carbon Fiber Reinforced Carbon–Al–Cu Composite for Friction Material

PubMed Central

Luo, Ruiying; Ma, Denghao

2018-01-01

A carbon/carbon–Al–Cu composite reinforced with carbon fiber 2.5D-polyacrylonitrile-based preforms was fabricated using the pressureless infiltration technique. The Al–Cu alloy liquids were successfully infiltrated into the C/C composites at high temperature and under vacuum. The mechanical and metallographic properties, scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy dispersive spectroscopy (EDS) of the C/C–Al–Cu composites were analyzed. The results showed that the bending property of the C/C–Al–Cu composites was 189 MPa, whereas that of the pure carbon slide material was only 85 MPa. The compressive strength of C/C–Al–Cu was 213 MPa, whereas that of the pure carbon slide material was only 102 MPa. The resistivity of C/C–Al–Cu was only 1.94 μΩm, which was lower than that of the pure carbon slide material (29.5 μΩm). This finding can be attributed to the “network conduction” structure. Excellent wettability was observed between Al and the carbon matrix at high temperature due to the existence of Al4C3. The friction coefficients of the C/C, C/C–Al–Cu, and pure carbon slide composites were 0.152, 0.175, and 0.121, respectively. The wear rate of the C/C–Al–Cu composites reached a minimum value of 2.56 × 10−7 mm3/Nm. The C/C–Al–Cu composite can be appropriately used as railway current collectors for locomotives. PMID:29614723

Carbon Fiber Reinforced Carbon-Al-Cu Composite for Friction Material.

PubMed

Cui, Lihui; Luo, Ruiying; Ma, Denghao

2018-03-31

A carbon/carbon-Al-Cu composite reinforced with carbon fiber 2.5D-polyacrylonitrile-based preforms was fabricated using the pressureless infiltration technique. The Al-Cu alloy liquids were successfully infiltrated into the C/C composites at high temperature and under vacuum. The mechanical and metallographic properties, scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy dispersive spectroscopy (EDS) of the C/C-Al-Cu composites were analyzed. The results showed that the bending property of the C/C-Al-Cu composites was 189 MPa, whereas that of the pure carbon slide material was only 85 MPa. The compressive strength of C/C-Al-Cu was 213 MPa, whereas that of the pure carbon slide material was only 102 MPa. The resistivity of C/C-Al-Cu was only 1.94 μΩm, which was lower than that of the pure carbon slide material (29.5 μΩm). This finding can be attributed to the "network conduction" structure. Excellent wettability was observed between Al and the carbon matrix at high temperature due to the existence of Al₄C₃. The friction coefficients of the C/C, C/C-Al-Cu, and pure carbon slide composites were 0.152, 0.175, and 0.121, respectively. The wear rate of the C/C-Al-Cu composites reached a minimum value of 2.56 × 10 -7 mm³/Nm. The C/C-Al-Cu composite can be appropriately used as railway current collectors for locomotives.

High-precision isotopic characterization of USGS reference materials by TIMS and MC-ICP-MS

NASA Astrophysics Data System (ADS)

Weis, Dominique; Kieffer, Bruno; Maerschalk, Claude; Barling, Jane; de Jong, Jeroen; Williams, Gwen A.; Hanano, Diane; Pretorius, Wilma; Mattielli, Nadine; Scoates, James S.; Goolaerts, Arnaud; Friedman, Richard M.; Mahoney, J. Brian

2006-08-01

The Pacific Centre for Isotopic and Geochemical Research (PCIGR) at the University of British Columbia has undertaken a systematic analysis of the isotopic (Sr, Nd, and Pb) compositions and concentrations of a broad compositional range of U.S. Geological Survey (USGS) reference materials, including basalt (BCR-1, 2; BHVO-1, 2), andesite (AGV-1, 2), rhyolite (RGM-1, 2), syenite (STM-1, 2), granodiorite (GSP-2), and granite (G-2, 3). USGS rock reference materials are geochemically well characterized, but there is neither a systematic methodology nor a database for radiogenic isotopic compositions, even for the widely used BCR-1. This investigation represents the first comprehensive, systematic analysis of the isotopic composition and concentration of USGS reference materials and provides an important database for the isotopic community. In addition, the range of equipment at the PCIGR, including a Nu Instruments Plasma MC-ICP-MS, a Thermo Finnigan Triton TIMS, and a Thermo Finnigan Element2 HR-ICP-MS, permits an assessment and comparison of the precision and accuracy of isotopic analyses determined by both the TIMS and MC-ICP-MS methods (e.g., Nd isotopic compositions). For each of the reference materials, 5 to 10 complete replicate analyses provide coherent isotopic results, all with external precision below 30 ppm (2 SD) for Sr and Nd isotopic compositions (27 and 24 ppm for TIMS and MC-ICP-MS, respectively). Our results also show that the first- and second-generation USGS reference materials have homogeneous Sr and Nd isotopic compositions. Nd isotopic compositions by MC-ICP-MS and TIMS agree to within 15 ppm for all reference materials. Interlaboratory MC-ICP-MS comparisons show excellent agreement for Pb isotopic compositions; however, the reproducibility is not as good as for Sr and Nd. A careful, sequential leaching experiment of three first- and second-generation reference materials (BCR, BHVO, AGV) indicates that the heterogeneity in Pb isotopic compositions, and concentrations, could be directly related to contamination by the steel (mortar/pestle) used to process the materials. Contamination also accounts for the high concentrations of certain other trace elements (e.g., Li, Mo, Cd, Sn, Sb, W) in various USGS reference materials.

Enhanced electrochemical performances with a copper/xylose-based carbon composite electrode

NASA Astrophysics Data System (ADS)

Sirisomboonchai, Suchada; Kongparakul, Suwadee; Nueangnoraj, Khanin; Zhang, Haibo; Wei, Lu; Reubroycharoen, Prasert; Guan, Guoqing; Samart, Chanatip

2018-04-01

Copper/carbon (Cu/C) composites were prepared through the simple and environmentally benign hydrothermal carbonization of xylose in the presence of Cu2+ ions. The morphology, specific surface area, phase structure and chemical composition were investigated. Using a three-electrode system in 0.1 M H2SO4 aqueous electrolyte, the Cu/C composite (10 wt% Cu) heat-treated at 600 °C gave the highest specific capacitance (316.2 and 350.1 F g-1 at 0.5 A g-1 and 20 mV s-1, respectively). The addition of Cu was the major factor in improving the electrochemical performance, enhancing the specific capacitance more than 30 times that of the C without Cu. Therefore, the Cu/C composite presented promising results in improving biomass-based C electrodes for supercapacitors.

Microcalorimetric and potentiometric titration studies on the adsorption of copper by extracellular polymeric substances (EPS), minerals and their composites.

PubMed

Fang, Linchuan; Huang, Qiaoyun; Wei, Xing; Liang, Wei; Rong, Xinming; Chen, Wenli; Cai, Peng

2010-08-01

Equilibrium adsorption experiments, isothermal titration calorimetry and potentiometric titration techniques were employed to investigate the adsorption of Cu(II) by extracellular polymeric substances (EPS) extracted from Pseudomonas putida X4, minerals (montmorillonite and goethite) and their composites. Compared with predicted values of Cu(II) adsorption on composites, the measured values of Cu(II) on EPS-montmorillonite composite increased, however, those on EPS-goethite composite decreased. Potentiometric titration results also showed that more surface sites were observed on EPS-montmorillonite composite and less reactive sites were found on EPS-goethite composite. The adsorption of Cu(II) on EPS molecules and their composites with minerals was an endothermic reaction, while that on minerals was exothermic. The positive values of enthalpy change (Delta H) and entropy change (DeltaS) for Cu(II) adsorption on EPS and mineral-EPS composites indicated that Cu(II) mainly interacts with carboxyl and phosphoryl groups as inner-sphere complexes on EPS molecules and their composites with minerals. (c) 2010 Elsevier Ltd. All rights reserved.

Feasibility of Isotope Harvesting at a Projectile Fragmentation Facility: 67Cu

DOE PAGES

Mastren, Tara; Pen, Aranh; Peaslee, Graham F.; ...

2014-10-21

The work presented here describes a proof-of-principle experiment for the chemical extraction of 67Cu from an aqueous beam stop at the National Superconducting Cyclotron Laboratory (NSCL). A 76 MeV/A 67Cu beam was stopped in water, successfully isolated from the aqueous solution through a series of chemical separations involving a chelating disk and anion exchange chromatography, then bound to NOTA-conjugated Herceptin antibodies, and the bound activity was validated using instant thin-layer chromatography (ITLC). The chemical extraction efficiency was found to be 88 ± 3% and the radiochemical yield was ≥95%. These results show that extraction of radioisotopes from an aqueous projectile-fragmentmore » beam dump is a feasible method for obtaining radiochemically pure isotopes.« less

Grain Refinement and Mechanical Properties of Cu-Cr-Zr Alloys with Different Nano-Sized TiCp Addition.

PubMed

Zhang, Dongdong; Bai, Fang; Wang, Yong; Wang, Jinguo; Wang, Wenquan

2017-08-08

The TiC p /Cu master alloy was prepared via thermal explosion reaction. Afterwards, the nano-sized TiC p /Cu master alloy was dispersed by electromagnetic stirring casting into the melting Cu-Cr-Zr alloys to fabricate the nano-sized TiC p -reinforced Cu-Cr-Zr composites. Results show that nano-sized TiC p can effectively refine the grain size of Cu-Cr-Zr alloys. The morphologies of grain in Cu-Cr-Zr composites changed from dendritic grain to equiaxed crystal because of the addition and dispersion of nano-sized TiC p . The grain size decreased from 82 to 28 μm with the nano-sized TiC p content. Compared with Cu-Cr-Zr alloys, the ultimate compressive strength (σ UCS ) and yield strength (σ 0.2 ) of 4 wt% TiC p -reinforced Cu-Cr-Zr composites increased by 6.7% and 9.4%, respectively. The wear resistance of the nano-sized TiCp-reinforced Cu-Cr-Zr composites increased with the increasing nano-sized TiCp content. The wear loss of the nano-sized TiC p -reinforced Cu-Cr-Zr composites decreased with the increasing TiC p content under abrasive particles. The eletrical conductivity of Cu-Cr-Zr alloys, 2% and 4% nano-sized TiCp-reinforced Cu-Cr-Zr composites are 64.71% IACS, 56.77% IACS and 52.93% IACS, respectively.

Synthesis of Cu-Fe{sub 3}O{sub 4}@graphene composite: A magnetically separable and efficient catalyst for the reduction of 4-nitrophenol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Ran; Bi, Huiping, E-mail: hpbi@njust.edu.cn; He, Guangyu

2014-09-15

Highlights: • The Cu-Fe{sub 3}O{sub 4}@GE composite was prepared by one-step solvent–thermal method. • The Cu-Fe{sub 3}O{sub 4}@GE composite exhibited the highest catalytic activity with excellent stability. • The Cu-Fe{sub 3}O{sub 4}@GE composite was magnetically separable. - Abstract: In this work, the Cu-Fe{sub 3}O{sub 4}@GE composite was prepared easily by a one-step solvent–thermal method, which achieved the formation of Cu nanoparticles (Cu NPs), Fe{sub 3}O{sub 4} nanoparticles (Fe{sub 3}O{sub 4} NPs) and reduction of GO simultaneously. The morphology and structure of the composite was fully characterized by means of X-ray diffraction (XRD), Fourier transformed infrared (FTIR) spectroscopy, transmission electron microscopymore » (TEM). The time-dependent adsorption spectra of the reaction mixture was measured by UV–vis absorption spectroscopy. The results demonstrated that the Cu NPs and Fe{sub 3}O{sub 4} NPs were densely and evenly deposited on the graphene (GE) sheets. It was found that the Cu-Fe{sub 3}O{sub 4}@GE composite exhibited high catalytic activities on the reduction of p-nitrophenol to p-aminophenol. Furthermore, the composite catalyst can be easily recovered due to its magnetic separability and high stability.« less

Microstructure and hardness of the Cu-SiC and Cu-diamond composites produced by vacuum hot pressing

NASA Astrophysics Data System (ADS)

Krishna, S. Chenna; Vikram, T.; Viswanath, S.; Subramanian, P. K.; Janardhana Reddy, J.

2018-03-01

In the present investigation, Cu-SiC and Cu-diamond composites with different volume percent of reinforcements were produced by vacuum hot pressing. Copper powder with different amount of SiC and diamond were hot pressed at 1000°C for 0.5 h at an applied pressure of 32 MPa. The achieved sintered density of the composites was in the range of 94-98 %. The sintered density decreased with an increase in the amount of SiC and diamond. Hardness of the composites improved with an increase in the volume percent of the reinforcements. Hardness of the Cu-30 vol.% diamond and Cu-30vol. % SiC composites was 88 VHN and 104 VHN, respectively.

Effects of Grain Orientation on Cu6Sn5 Growth Behavior in Cu6Sn5-Reinforced Composite Solder Joints During Electromigration

NASA Astrophysics Data System (ADS)

Han, Jing; Wang, Yan; Tan, Shihai; Guo, Fu

2018-02-01

Electromigration is a major reliability problem in composite solder joints. Due to the anisotropy of the β-Sn crystal structure, the Sn grain orientations present in the solder matrix dominate the principal failure mechanism in solder joints under electric current stressing. In this work, the Cu6Sn5 growth behavior in Cu6Sn5-reinforced composite solder joints with three different Sn grain orientations was investigated at current density of 104 A/cm2 at room temperature. Micron-sized Cu particles were added to Sn-3.5Ag solder at 2% volume fraction using an in situ method. After current stressing for 528 h, the polarity effect in the composite solder joint was greatest for an angle ( θ) between the c-axis and electron flow direction of 30°, resulting in higher growth rate of Cu6Sn5 in the solder matrix compared with composite solder joints with θ of 60° or 90°. There were no noticeable changes in the composite solder joint with θ of 90°. The growth behavior of Cu6Sn5, Cu atomic motion, and Cu diffusivity in the composite solder joints with different Sn grain orientations were analyzed in detail.

Visible light-driven photocatalytic H{sub 2}-generation activity of CuS/ZnS composite particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiao, Liang; Chen, Hua; Huang, Jianhua, E-mail: jhhuang@zstu.edu.cn

2015-04-15

Highlights: • Preparation of CuS/ZnS composite photocatalyst by cation-exchange reaction. • Visible light photocatalytic activity for H{sub 2} evolution without cocatalyst. • The H{sub 2}-evolution rate from water splitting depends on the CuS content. • The highest rate of H{sub 2} evolution is obtained with CuS (0.5 mol%)/ZnS composite. - Abstract: CuS/ZnS composite particles with diameter of 200–400 nm were successfully prepared by a simple cation-exchange reaction using ZnS spheres as a precursor. CuS nanoparticles with a few nanometers in diameter were observed on the surface of composite particles. The synthesized CuS/ZnS composite particles showed photocatalytic property effective for H{submore » 2} evolution from an aqueous Na{sub 2}S and Na{sub 2}SO{sub 3} solution under visible light irradiation without any cocatalysts. The rate of H{sub 2} generation was found to be strongly dependent on the CuS content. The highest rate of H{sub 2} evolution reached 695.7 μmol h{sup −1} g{sup −1}, which was almost 7 times as high as that of the mechanical mixture of CuS and ZnS. The enhancement in the photocatalytic activity of CuS/ZnS composite particles is supposed to be due to the direct interfacial charge transfer of the CuS/ZnS heterojunction.« less

Converting isotope ratios to diet composition - the use of mixing models - June 2010

EPA Science Inventory

One application of stable isotope analysis is to reconstruct diet composition based on isotopic mass balance. The isotopic value of a consumer’s tissue reflects the isotopic values of its food sources proportional to their dietary contributions. Isotopic mixing models are used ...

Cu-67 Photonuclear Production

NASA Astrophysics Data System (ADS)

Starovoitova, Valeriia; Foote, Davy; Harris, Jason; Makarashvili, Vakhtang; Segebade, Christian R.; Sinha, Vaibhav; Wells, Douglas P.

2011-06-01

Cu-67 is considered as one of the most promising radioisotopes for cancer therapy with monoclonal antibodies. Current production schemes using high-flux reactors and cyclotrons do not meet potential market need. In this paper we discuss Cu-67 photonuclear production through the reaction Zn-68(γ,p)Cu-67. Computer simulations were done together with experiments to study and optimize Cu-67 yield in natural Zn target. The data confirms that the photonuclear method has potential to produce large quantities of the isotope with sufficient purity to be used in medical field.

What is needed to understand feedback mechanisms from agricultural and climate changes that can alter the hydrological system and the transport of sediments and agricultural chemicals?

NASA Astrophysics Data System (ADS)

Coupe, Richard; Payraudeau, Sylvain; Babcsányi, Izabella; Imfeld, Gwenaël

2015-04-01

Modern agriculture activities are constantly changing as producers try to produce a crop, keep their soils fertile, control pests, and prevent contamination of air and water resources. Because most of the world's arable land is already in production we must become more efficient if we are to feed and clothe the world's growing population as well as do this in a sustainable manner; leaving a legacy of fertile soil and clean water resources for our descendants. The objective of this paper is to demonstrate the importance of historical datasets and of developing new strategies to understand the effects of changing agricultural systems on the environment. Scientists who study agriculture and its effects on water must constantly adapt their strategies and evaluate how changing agricultural activities impact the environment. As well as understand from historical datasets on hydrology and agriculture how a changing climate or agricultural activity such as a change in tillage method might impact the processes that determine the movement of agricultural chemicals off of the target site. The 42.7 ha Hohrain (Rouffach, Alsace, France) vineyard experimental catchment offers several examples of how scientists have used historical data from this catchment to understand how the transport of agricultural chemicals may change due to a changing climate as well as how new strategies are developed for understanding the transport of agricultural chemicals. Runoff is a major process of pesticide transport from agricultural land to downstream aquatic ecosystems. The impact of rainfall characteristics on the transport of runoff-related pesticides is crucial to understanding how to prevent or minimize their movement now, but also in understanding how climate change might affect runoff. If we understand how rainfall characteristics affect the transport of pesticides, we can use climate change models to predict how those characteristics might change in the future and be better prepared for those changes. Recent analytical developments in the stable isotope analysis techniques have allowed the use of Cu isotopes as a tool to better understand the fate of copper in the environment. Copper (Cu) has long been used in agriculture mainly as a fungicide authorized in organic farming. Vineyards may become Cu-contaminated because large quantities of Cu are applied yearly (up to 6 kg ha-1 in the European Union) resulting in topsoil Cu concentrations in vineyards of 15 to 3200 mg/kg. Large amounts of Cu are removed from agricultural land by runoff and erosion, and this Cu may eventually contaminate aquatic ecosystems. The stable isotopes of Cu (65Cu/63Cu) are potentially powerful geochemical tracers for transport and transformation processes of anthropogenic Cu. Proof of concept work is underway in the Rouffach catchment to determine if the stable isotopes of Cu can be useful in understanding how changes in hydrology affect the transport of metals.

Graphene-copper composite with micro-layered grains and ultrahigh strength

PubMed Central

Wang, Lidong; Yang, Ziyue; Cui, Ye; Wei, Bing; Xu, Shichong; Sheng, Jie; Wang, Miao; Zhu, Yunpeng; Fei, Weidong

2017-01-01

Graphene with ultrahigh intrinsic strength and excellent thermal physical properties has the potential to be used as the reinforcement of many kinds of composites. Here, we show that very high tensile strength can be obtained in the copper matrix composite reinforced by reduced graphene oxide (RGO) when micro-layered structure is achieved. RGO-Cu powder with micro-layered structure is fabricated from the reduction of the micro-layered graphene oxide (GO) and Cu(OH)2 composite sheets, and RGO-Cu composites are sintered by spark plasma sintering process. The tensile strength of the 5 vol.% RGO-Cu composite is as high as 608 MPa, which is more than three times higher than that of the Cu matrix. The apparent strengthening efficiency of RGO in the 2.5 vol.% RGO-Cu composite is as high as 110, even higher than that of carbon nanotube, multilayer graphene, carbon nano fiber and RGO in the copper matrix composites produced by conventional MLM method. The excellent tensile and compressive strengths, high hardness and good electrical conductivity are obtained simultaneously in the RGO-Cu composites. The results shown in the present study provide an effective method to design graphene based composites with layered structure and high performance. PMID:28169306

Effective charge separation in BiOI/Cu2O composites with enhanced photocatalytic activity

NASA Astrophysics Data System (ADS)

Xia, Yongmei; He, Zuming; Yang, Wei; Tang, Bin; Lu, Yalin; Hu, Kejun; Su, Jiangbin; Li, Xiaoping

2018-02-01

Novel BiOI/Cu2O composites were designed and synthesized for the first time by coupling reduction method at low temperature. The samples were characterized by XRD, XPS, SEM, EDS, HRTEM, UV-vis (DRS), FTIR and photo-electro-chemical (PEC) analysis. Results showed that the BiOI/Cu2O composites consisted of three-dimensional (3D), hierarchical cauliflower-like structure composed of BiOI nanosheet and Cu2O cubic submicrometer structure, the composite absorption band broadened, and the absorption intensity in the visible region strengthened. And the composites exhibited an excellent photocatalytic performance, which might be attributed to the improvement of the composite absorption and effective charge separation in BiOI/Cu2O composites. In addition, the possible photocatalytic mechanism was proposed.

Facile synthesis of core-shell Cu2O@ ZnO structure with enhanced photocatalytic H2 production

NASA Astrophysics Data System (ADS)

Zhang, Yong-Hui; Jiu, Bei-Bei; Gong, Fei-Long; Lu, Kuan; Jiang, Nan; Zhang, Hao-Li; Chen, Jun-Li

2018-05-01

Core-shell Cu2O@ZnO composites were synthesized successfully based on a one-pot hydrothermal method in the presence of dioctyl sulfosuccinate sodium salt (AOT) surfactant. The Cu2O can be converted to rough core-shell Cu2O@ZnO structure by adjusting the amount of zinc powder added. The as-synthesized Cu2O@ZnO composites exhibited excellent photocatalytic activity and the amount of H2 generated using these composites was 4.5-fold more than that produced with Cu2O cubes. A possible photocatalytic mechanism for the Cu2O@ZnO composites with enhanced photocatalytic activity could be the separation by ZnO of the effective charge carriers.

Facile synthesis of CuFe2O4-Fe2O3 composite for high-performance supercapacitor electrode applications

NASA Astrophysics Data System (ADS)

Khan, Rashid; Habib, Muhammad; Gondal, Mohammed A.; Khalil, Adnan; Rehman, Zia Ur; Muhammad, Zahir; Haleem, Yasir A.; Wang, Changda; Wu, Chuan Qiang; Song, Li

2017-10-01

We report the synthesis of CuFe2O4-Fe2O3 composite material for efficient and highly stable supercapacitor electrode by using eco-friendly low-temperature co-precipitation method. The CuFe2O4-Fe2O3 composite demonstrated the highest specific capacitance of 638.24 F g-1 and excellent stability up to 2000 charge/discharge cycles. The achieved capacitance value is 16 times higher than that of pure CuFe2O4. The results revealed the extraordinary performance of CuFe2O4-Fe2O3 composite as supercapacitor electrode with excellent retention in comparison to CuFe2O4. The enhanced electrochemical activity of CuFe2O4-Fe2O3 composite is attributed to the synergistic effect which is responsible for redox coupling between Cu2+ and Fe3+ that has never been achieved by single component before.

Copper-polydopamine composite derived from bioinspired polymer coating

DOE PAGES

Zhao, Yao; Wang, Hsin; Qian, Bosen; ...

2018-04-01

Metal matrix composites with nanocarbon phases, such carbon nanotube (CNT) and graphene, have shown potentials to achieve improved mechanical, thermal, and electrical properties. However, incorporation of these nanocarbons into the metal matrix usually involves complicated processes. Here, this study explored a new processing method to fabricate copper (Cu) matrix composite by coating Cu powder particles with nanometer-thick polydopamine (PDA) thin films and sintering of the powder compacts. For sintering temperatures between 300°C and 750°C, the Cu-PDA composite samples showed higher electrical conductivity and thermal conductivity than the uncoated Cu samples, which is likely related to the higher mass densities ofmore » the composite samples. After being sintered at 950°C, the thermal conductivity of the Cu-PDA sample was approximately 12% higher than the Cu sample, while the electrical conductivity did not show significant difference. On the other hand, Knoop micro-hardness values were comparable between the Cu-PDA and Cu samples sintered at the same temperatures.« less

Copper-polydopamine composite derived from bioinspired polymer coating

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Yao; Wang, Hsin; Qian, Bosen

Metal matrix composites with nanocarbon phases, such carbon nanotube (CNT) and graphene, have shown potentials to achieve improved mechanical, thermal, and electrical properties. However, incorporation of these nanocarbons into the metal matrix usually involves complicated processes. Here, this study explored a new processing method to fabricate copper (Cu) matrix composite by coating Cu powder particles with nanometer-thick polydopamine (PDA) thin films and sintering of the powder compacts. For sintering temperatures between 300°C and 750°C, the Cu-PDA composite samples showed higher electrical conductivity and thermal conductivity than the uncoated Cu samples, which is likely related to the higher mass densities ofmore » the composite samples. After being sintered at 950°C, the thermal conductivity of the Cu-PDA sample was approximately 12% higher than the Cu sample, while the electrical conductivity did not show significant difference. On the other hand, Knoop micro-hardness values were comparable between the Cu-PDA and Cu samples sintered at the same temperatures.« less

Microstructure and Mechanical Behavior of Microwave Sintered Cu50Ti50 Amorphous Alloy Reinforced Al Metal Matrix Composites

NASA Astrophysics Data System (ADS)

Reddy, M. Penchal; Ubaid, F.; Shakoor, R. A.; Mohamed, A. M. A.

2018-06-01

In the present work, Al metal matrix composites reinforced with Cu-based (Cu50Ti50) amorphous alloy particles synthesized by ball milling followed by a microwave sintering process were studied. The amorphous powders of Cu50Ti50 produced by ball milling were used to reinforce the aluminum matrix. They were examined by x-ray diffraction (XRD), scanning electron microscopy (SEM), microhardness and compression testing. The analysis of XRD patterns of the samples containing 5 vol.%, 10 vol.% and 15 vol.% Cu50Ti50 indicates the presence of Al and Cu50Ti50 peaks. SEM images of the sintered composites show the uniform distribution of reinforced particles within the matrix. Mechanical properties of the composites were found to increase with an increasing volume fraction of Cu50Ti50 reinforcement particles. The hardness and compressive strength were enhanced to 89 Hv and 449 MPa, respectively, for the Al-15 vol.% Cu50Ti50 composites.

Achieving high strength and high ductility in metal matrix composites reinforced with a discontinuous three-dimensional graphene-like network.

PubMed

Zhang, Xiang; Shi, Chunsheng; Liu, Enzuo; He, Fang; Ma, Liying; Li, Qunying; Li, Jiajun; Bacsa, Wolfgang; Zhao, Naiqin; He, Chunnian

2017-08-24

Graphene or graphene-like nanosheets have been emerging as an attractive reinforcement for composites due to their unique mechanical and electrical properties as well as their fascinating two-dimensional structure. It is a great challenge to efficiently and homogeneously disperse them within a metal matrix for achieving metal matrix composites with excellent mechanical and physical performance. In this work, we have developed an innovative in situ processing strategy for the fabrication of metal matrix composites reinforced with a discontinuous 3D graphene-like network (3D GN). The processing route involves the in situ synthesis of the encapsulation structure of 3D GN powders tightly anchored with Cu nanoparticles (NPs) (3D GN@Cu) to ensure mixing at the molecular level between graphene-like nanosheets and metal, coating of Cu on the 3D GN@Cu (3D GN@Cu@Cu), and consolidation of the 3D GN@Cu@Cu powders. This process can produce GN/Cu composites on a large scale, in which the in situ synthesized 3D GN not only maintains the perfect 3D network structure within the composites, but also has robust interfacial bonding with the metal matrix. As a consequence, the as-obtained 3D GN/Cu composites exhibit exceptionally high strength and superior ductility (the uniform and total elongation to failure of the composite are even much higher than the unreinforced Cu matrix). To the best of our knowledge, this work is the first report validating that a discontinuous 3D graphene-like network can simultaneously remarkably enhance the strength and ductility of the metal matrix.

Electroless Cu/Ni Plating on Graphite Flake and the Effects to the Properties of Graphite Flake/Si/Al Hybrid Composites

NASA Astrophysics Data System (ADS)

Huang, Ying; Peng, Xuanyi; Yang, Yiwen; Wu, Haiwei; Sun, Xu; Han, Xiaopeng

2018-03-01

Proper process and parameter were investigated to coat Cu or Ni on graphite flake (Gf) by electroless plating. Microstructural characterization indicated that the Cu/Ni was coated on the Gf uniformly and comprehensively. Then aluminum matrix composites reinforced with Si and graphite were fabricated by a unique vacuum gas pressure infiltration. The thermal conductivity and mechanical properties of the composites, both with and without Cu or Ni coating layers on the graphite surface, have been studied. The obtained results indicated that the mechanical property of the Cu or Ni coated Gf/Si/Al composites dramatically increased, as compared with the non-coated Gf/Si/Al composite. In the meantime, Cu or Ni coated Gf proved to have better wettability and interfacial bonding with the aluminum matrix, which were expected to be a highly sustainable and dispersible reinforcement for metal matrix composites.

Preparation of Advanced CuO Nanowires/Functionalized Graphene Composite Anode Material for Lithium Ion Batteries.

PubMed

Zhang, Jin; Wang, Beibei; Zhou, Jiachen; Xia, Ruoyu; Chu, Yingli; Huang, Jia

2017-01-17

The copper oxide (CuO) nanowires/functionalized graphene (f-graphene) composite material was successfully composed by a one-pot synthesis method. The f-graphene synthesized through the Birch reduction chemistry method was modified with functional group "-(CH₂)₅COOH", and the CuO nanowires (NWs) were well dispersed in the f-graphene sheets. When used as anode materials in lithium-ion batteries, the composite exhibited good cyclic stability and decent specific capacity of 677 mA·h·g -1 after 50 cycles. CuO NWs can enhance the lithium-ion storage of the composites while the f-graphene effectively resists the volume expansion of the CuO NWs during the galvanostatic charge/discharge cyclic process, and provide a conductive paths for charge transportation. The good electrochemical performance of the synthesized CuO/f-graphene composite suggests great potential of the composite materials for lithium-ion batteries anodes.

The importance of carbon nanotube wire density, structural uniformity, and purity for fabricating homogeneous carbon nanotube-copper wire composites by copper electrodeposition

NASA Astrophysics Data System (ADS)

Sundaram, Rajyashree; Yamada, Takeo; Hata, Kenji; Sekiguchi, Atsuko

2018-04-01

We present the influence of density, structural regularity, and purity of carbon nanotube wires (CNTWs) used as Cu electrodeposition templates on fabricating homogeneous high-electrical performance CNT-Cu wires lighter than Cu. We show that low-density CNTWs (<0.6 g/cm3 for multiwall nanotube wires) with regular macro- and microstructures and high CNT content (>90 wt %) are essential for making homogeneous CNT-Cu wires. These homogeneous CNT-Cu wires show a continuous Cu matrix with evenly mixed nanotubes of high volume fractions (˜45 vol %) throughout the wire-length. Consequently, the composite wires show densities ˜5.1 g/cm3 (33% lower than Cu) and electrical conductivities ˜6.1 × 104 S/cm (>100 × CNTW conductivity). However, composite wires from templates with higher densities or structural inconsistencies are non-uniform with discontinuous Cu matrices and poor CNT/Cu mixing. These non-uniform CNT-Cu wires show conductivities 2-6 times lower than the homogeneous composite wires.

Performance and optimization of a combustion interface for isotope ratio monitoring gas chromatography/mass spectrometry

NASA Technical Reports Server (NTRS)

Merritt, D. A.; Freeman, K. H.; Ricci, M. P.; Studley, S. A.; Hayes, J. M.

1995-01-01

Conditions and systems for on-line combustion of effluents from capillary gas chromatographic columns and for removal of water vapor from product streams were tested. Organic carbon in gas chromatographic peaks 15 s wide and containing up to 30 nanomoles of carbon was quantitatively converted to CO2 by tubular combustion reactors, 200 x 0.5 mm, packed with CuO or NiO. No auxiliary source of O2 was required because oxygen was supplied by metal oxides. Spontaneous degradation of CuO limited the life of CuO reactors at T > 850 degrees C. Since NiO does not spontaneously degrade, its use might be favored, but Ni-bound carbon phases form and lead to inaccurate isotopic results at T < 1050 degrees C if gas-phase O2 is not added. For all compounds tested except CH4, equivalent isotopic results are provided by CuO at 850 degrees C, NiO + O2 (gas-phase mole fraction, 10(-3)) at 1050 degrees C and NiO at 1150 degrees C. The combustion interface did not contribute additional analytical uncertainty, thus observed standard deviations of 13C/12C ratios were within a factor of 2 of shot-noise limits. For combustion and isotopic analyses of CH4, in which quantitative combustion required T approximately 950 degrees C, NiO-based systems are preferred, and precision is approximately 2 times lower than that observed for other analytes. Water must be removed from the gas stream transmitted to the mass spectrometer or else protonation of CO2 will lead to inaccuracy in isotopic analyses. Although thresholds for this effect vary between mass spectrometers, differential permeation of H2O through Nafion tubing was effective in both cases tested, but the required length of the Nafion membrane was 4 times greater for the more sensitive mass spectrometer.

Performance and optimization of a combustion interface for isotope ratio monitoring gas chromatography/mass spectrometry.

PubMed

Merritt, D A; Freeman, K H; Ricci, M P; Studley, S A; Hayes, J M

1995-07-15

Conditions and systems for on-line combustion of effluents from capillary gas chromatographic columns and for removal of water vapor from product streams were tested. Organic carbon in gas chromatographic peaks 15 s wide and containing up to 30 nanomoles of carbon was quantitatively converted to CO2 by tubular combustion reactors, 200 x 0.5 mm, packed with CuO or NiO. No auxiliary source of O2 was required because oxygen was supplied by metal oxides. Spontaneous degradation of CuO limited the life of CuO reactors at T > 850 degrees C. Since NiO does not spontaneously degrade, its use might be favored, but Ni-bound carbon phases form and lead to inaccurate isotopic results at T < 1050 degrees C if gas-phase O2 is not added. For all compounds tested except CH4, equivalent isotopic results are provided by CuO at 850 degrees C, NiO + O2 (gas-phase mole fraction, 10(-3)) at 1050 degrees C and NiO at 1150 degrees C. The combustion interface did not contribute additional analytical uncertainty, thus observed standard deviations of 13C/12C ratios were within a factor of 2 of shot-noise limits. For combustion and isotopic analyses of CH4, in which quantitative combustion required T approximately 950 degrees C, NiO-based systems are preferred, and precision is approximately 2 times lower than that observed for other analytes. Water must be removed from the gas stream transmitted to the mass spectrometer or else protonation of CO2 will lead to inaccuracy in isotopic analyses. Although thresholds for this effect vary between mass spectrometers, differential permeation of H2O through Nafion tubing was effective in both cases tested, but the required length of the Nafion membrane was 4 times greater for the more sensitive mass spectrometer.

High strength-high conductivity Cu--Fe composites produced by powder compaction/mechanical reduction

DOEpatents

Verhoeven, John D.; Spitzig, William A.; Gibson, Edwin D.; Anderson, Iver E.

1991-08-27

A particulate mixture of Cu and Fe is compacted and mechanically reduced to form an "in-situ" Cu-Fe composite having high strength and high conductivity. Compaction and mechanical reduction of the particulate mixture are carried out at a temperature and time at temperature selected to avoid dissolution of Fe into the Cu matrix particulates to a harmful extent that substantially degrades the conductivity of the Cu-Fe composite.

Post-collisional alkaline magmatism as gateway for metal and sulfur enrichment of the continental lower crust

NASA Astrophysics Data System (ADS)

Fiorentini, Marco L.; LaFlamme, Crystal; Denyszyn, Steven; Mole, David; Maas, Roland; Locmelis, Marek; Caruso, Stefano; Bui, Thi-Hao

2018-02-01

Mafic and ultramafic magmas that intrude into the lower crust can preserve evidence for metal and sulfur transfer from the lithospheric mantle into the lower continental crust. Here we focus on a series of ultramafic, alkaline pipes in the Ivrea Zone (NW Italy), which exposes deeply buried (6-11 kbar), migmatitic metasedimentary rocks intruded by voluminous basaltic magmas of the Mafic Complex, a major crustal underplating event precisely dated via U/Pb CA-IDTIMS on zircon at 286.8 ± 0.4 Ma. The ultramafic pipes postdate the Mafic Complex and from 100 to 300 m wide cumulate-rich conduits. They are hydrated and carbonated, have unusually high incompatible element concentrations and contain blebby and semi-massive Ni-Cu-PGE sulfide mineralisation. The sulfides occur as coarse intergranular nodules (>10 mm) and as small intragranular blebs (<1 mm) hosted in olivine, and have homogeneous, mantle-like δ34S (+1.35 ± 0.25‰). This homogeneity suggests that the pipes reached sulfide supersaturation without addition of crustal sulfur, and that the δ34S signature is representative of the continental lithospheric mantle. One of the pipes, the 249 Ma Valmaggia pipe, carries a very distinctive Sr-Nd-Hf-Pb isotopic composition in its core (87Sr/86Sr 0.70250, εNd-18, εHf-18, 206Pb/204Pb 16.0, 207Pb/204Pb 15.16, 208Pb/204Pb 35.87), very different from the margin of this pipe and from other pipes that have higher 87Sr/86Sr, εNd and 206Pb/204Pb. The unusual isotopic composition of the Valmaggia pipe requires a source with long-term (2500-1500 million years) U-, Th- and Rb-depletion and LREE enrichment. Such compositions are found in Late Archean/Early Proterozoic granulites and lower crustal xenoliths. We suggest that the unusual isotopic composition of the Valmaggia pipe reflects contamination of the mantle source of the pipe with a crustal component that is neither represented in the local Paleozoic crust nor in the isotopically anomalous hydrated mantle inferred as the source of the large-volume mafic underplate that formed the Mafic Complex. During post-collisional gravitational collapse of the Variscan Orogen, this source produced the alkaline, metal (Ni, Cu, PGE)- and volatile (H2O, CO2, S)-rich mafic-ultramafic magma that formed the deep-crustal intrusion at Valmaggia. U/Pb dating of other chemically and geologically comparable pipes in the area shows that this process was active over at least 40 Ma. The Ivrea pipes illustrate how the lower continental crust can be fertilised with mantle-derived metals and volatiles, which are available for later remobilisation into upper-crustal ore systems. World-class mineral deposits along the margins of lithospheric blocks may thus be the result of both favourable crustal architecture (focussing of magmas and fluids) and localised volatile and metal enrichment of the lower crust related to mantle-derived hydrous metasomatism.

Controlling intermetallic compound growth in SnAgCu/Ni-P solder joints by nanosized Cu6Sn5 addition

NASA Astrophysics Data System (ADS)

Kao, Szu-Tsung; Lin, Yung-Chi; Duh, Jenq-Gong

2006-03-01

Nanosized Cu6Sn5 dispersoids were incorporated into Sn and Ag powders and milled together to form Sn-3Ag-0.5Cu composite solders by a mechanical alloying process. The aim of this study was to investigate the interfacial reaction between SnAgCu composite solder and electroless Ni-P/Cu UBM after heating for 15 min. at 240°C. The growth of the IMCs formed at the composite solder/EN interface was retarded as compared to the commercial Sn3Ag0.5Cu solder joints. With the aid of the elemental distribution by x-ray color mapping in electron probe microanalysis (EPMA), it was revealed that the SnAgCu composite solder exhibited a refined structure. It is proposed that the Cu6Sn5 additives were pinned on the grain boundary of Sn after heat treatment, which thus retarded the movement of Cu toward the solder/EN interface to form interfacial compounds. In addition, wetting is an essential prerequisite for soldering to ensure good bonding between solder and substrate. It was demonstrated that the contact angles of composite solder paste was <25°, and good wettability was thus assured.

Microstructures and Properties of 40Cu/Ag(Invar) Composites Fabricated by Powder Metallurgy and Subsequent Thermo-Mechanical Treatment

NASA Astrophysics Data System (ADS)

Zhang, Xin; Huang, Yingqiu; Liu, Xiangyu; Yang, Lei; Shi, Changdong; Wu, Yucheng; Tang, Wenming

2018-03-01

Composites of 40Cu/Ag(Invar) were prepared via pressureless sintering and subsequent thermo-mechanical treatment from raw materials of electroless Ag-plated Invar alloy powder and electrolytic Cu powder. Microstructures and properties of the prepared composites were studied to evaluate the effect of the Ag layer on blocking Cu/Invar interfacial diffusion in the composites. The electroless-plated Ag layer was dense, uniform, continuous, and bonded tightly with the Invar alloy substrate. During sintering of the composites, the Ag layer effectively prevented Cu/Invar interfacial diffusion. During cold-rolling, the Ag layer was deformed uniformly with the Invar alloy particles. The composites exhibited bi-continuous network structure and considerably improved properties. After sintering at 775 °C and subsequent thermo-mechanical treatment, the 40Cu/Ag(Invar) composites showed satisfactory comprehensive properties: relative density of 99.0 pct, hardness of HV 253, thermal conductivity of 55.7 W/(m K), and coefficient of thermal expansion of 11.2 × 10-6/K.

Origin of placer laurite from Borneo: Se and As contents, and S isotopic compositions

USGS Publications Warehouse

Hattori, K.H.; Cabri, L.J.; Johanson, B.; Zientek, M.L.

2004-01-01

We examined grains of the platinum-group mineral, laurite (RuS2), from the type locality, Pontyn River, Tanah Laut, Borneo, and from the Tambanio River, southeast Borneo. The grains show a variety of morphologies, including euhedral grains with conchoidal fractures and pits, and spherical grains with no crystal faces, probably because of abrasion. Inclusions are rare, but one grain contains Ca-Al amphilbole inclusions, and another contains an inclusion of chalcopyrite+bornite+pentlandite+heazlewoodite (Ni3S2) that is considered to have formed by a two-stage process of exsolution and crystallization from a once homogeneous Fe-Cu-Ni sulphide melt. All grains examined are solid solutions of Ru and Os with Ir (2.71-11.76 wt.%) and Pd (0.31-0.66 wt%). Their compositions are similar to laurite from ophiolitic rocks. The compositions show broad negative correlations between Os and Ir, between As and Ir, and between As (0.4-0.74 wt.%) and Se (140 to 240 ppm). Laurite with higher Os contains more Se and less Ir and As. The negative correlations between Se and As may be attributed to their occupancy of the S site, but the compositional variations of Os. Ir and As probably reflect the compositional variation of rocks where the crystals grew. Ratios of S/Se in laurite show a narrow spread from 1380 to 2300, which are similar to ratios for sulphides from the refractory sub-are mantle. Sulphur isotopic compositions of laurite are independent of chemical compositions and morphologies and are similar to the chondritic value of 0???. The data suggest that S in laurite has not undergone redox changes and originated from the refractory mantle. The data support the formation of laurite in the residual mantle or in a magnia generated from such a refractory mantle, followed by erosion after the obduction of the host ultramafic rocks. ?? 2004 The Mineralogical Society.

Effects of climatic seasonality on the isotopic composition of evaporating soil waters

NASA Astrophysics Data System (ADS)

Benettin, Paolo; Volkmann, Till H. M.; von Freyberg, Jana; Frentress, Jay; Penna, Daniele; Dawson, Todd E.; Kirchner, James W.

2018-05-01

Stable water isotopes are widely used in ecohydrology to trace the transport, storage, and mixing of water on its journey through landscapes and ecosystems. Evaporation leaves a characteristic signature on the isotopic composition of the water that is left behind, such that in dual-isotope space, evaporated waters plot below the local meteoric water line (LMWL) that characterizes precipitation. Soil and xylem water samples can often plot below the LMWL as well, suggesting that they have also been influenced by evaporation. These soil and xylem water samples frequently plot along linear trends in dual-isotope space. These trend lines are often termed "evaporation lines" and their intersection with the LMWL is often interpreted as the isotopic composition of the precipitation source water. Here we use numerical experiments based on established isotope fractionation theory to show that these trend lines are often by-products of the seasonality in evaporative fractionation and in the isotopic composition of precipitation. Thus, they are often not true evaporation lines, and, if interpreted as such, can yield highly biased estimates of the isotopic composition of the source water.

Baseline shifts in coral skeletal oxygen isotopic composition: a signature of symbiont shuffling?

NASA Astrophysics Data System (ADS)

Carilli, J. E.; Charles, C. D.; Garren, M.; McField, M.; Norris, R. D.

2013-06-01

Decades-long records of the stable isotopic composition of coral skeletal cores were analyzed from four sites on the Mesoamerican Reef. Two of the sites exhibited baseline shifts in oxygen isotopic composition after known coral bleaching events. Changes in pH at the calcification site caused by a change in the associated symbiont community are invoked to explain the observed shift in the isotopic composition. To test the hypothesis that changes in symbiont clade could affect skeletal chemistry, additional coral samples were collected from Belize for paired Symbiodinium identification and skeletal stable isotopic analysis. We found some evidence that skeletal stable isotopic composition may be affected by symbiont clade and suggest this is an important topic for future investigation. If different Symbiodinium clades leave consistent signatures in skeletal geochemical composition, the signature will provide a method to quantify past symbiont shuffling events, important for understanding how corals are likely to respond to climate change.

Segregation at the surfaces of CuxPd1-x alloys in the presence of adsorbed S

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, James B.; Priyadarshini, Deepika; Gellman, Andrew J.

2012-10-01

The influence of adsorbed S on surface segregation in Cu{sub x}Pd{sub 1 - x} alloys (S/Cu{sub x}Pd{sub 1 - x)} was characterized over a wide range of bulk alloy compositions (x = 0.05 to 0.95) using high-throughput Composition Spread Alloy Film (CSAF) sample libraries. Top-surface and near-surface compositions of the CSAFs were measured as functions of bulk Cu composition, x, and temperature using spatially resolved low energy ion scattering spectroscopy (LEISS) and X-ray photoemission spectroscopy (XPS). Preferential segregation of Cu to the top-surface of the S/Cu{sub x}Pd{sub 1 - x} CSAF was observed at all bulk compositions, x, but themore » extent of Cu segregation to the S/Cu{sub x}Pd{sub 1 - x} surface was lower than the Cu segregation to the surface of a clean Cu{sub x}Pd{sub 1 - x} CSAF, clear evidence of an S-induced “segregation reversal.” The Langmuir–McLean formulation of the Gibbs isotherm was used to estimate the enthalpy and entropy of Cu segregation to the top-surface, ΔH{sub seg}(x) and ΔS{sub seg}(x), at saturation sulfur coverages. While Cu segregation to the top-surface of the clean Cu{sub x}Pd{sub 1 - x} is exothermic (ΔH{sub seg} < 0) for all bulk Cu compositions, it is endothermic (ΔH{sub seg} > 0) for S/Cu{sub x}Pd{sub 1 - x}. Segregation to the S/Cu{sub x}Pd{sub 1 - x} surface is driven by entropy. Changes in segregation patterns that occur upon adsorption of S onto Cu{sub x}Pd{sub 1 - x} appear to be related to formation of energetically favored Pd{single bond}S bonds at the surface, which counterbalance the enthalpic driving forces for Cu segregation to the clean surface.« less

Sintering behavior and thermal conductivity of nickel-coated graphite flake/copper composites fabricated by spark plasma sintering

NASA Astrophysics Data System (ADS)

Xu, Hui; Chen, Jian-hao; Ren, Shu-bin; He, Xin-bo; Qu, Xuan-hui

2018-04-01

Nickel-coated graphite flakes/copper (GN/Cu) composites were fabricated by spark plasma sintering with the surface of graphite flakes (GFs) being modified by Ni-P electroless plating. The effects of the phase transition of the amorphous Ni-P plating and of Ni diffusion into the Cu matrix on the densification behavior, interfacial microstructure, and thermal conductivity (TC) of the GN/Cu composites were systematically investigated. The introduction of Ni-P electroless plating efficiently reduced the densification temperature of uncoated GF/Cu composites from 850 to 650°C and slightly increased the TC of the X-Y basal plane of the GF/Cu composites with 20vol%-30vol% graphite flakes. However, when the graphite flake content was greater than 30vol%, the TC of the GF/Cu composites decreased with the introduction of Ni-P plating as a result of the combined effect of the improved heat-transfer interface with the transition layer, P generated at the interface, and the diffusion of Ni into the matrix. Given the effect of the Ni content on the TC of the Cu matrix and on the interface thermal resistance, a modified effective medium approximation model was used to predict the TC of the prepared GF/Cu composites.

Archival processes of the water stable isotope signal in East Antarctic ice cores

NASA Astrophysics Data System (ADS)

Casado, Mathieu; Landais, Amaelle; Picard, Ghislain; Münch, Thomas; Laepple, Thomas; Stenni, Barbara; Dreossi, Giuliano; Ekaykin, Alexey; Arnaud, Laurent; Genthon, Christophe; Touzeau, Alexandra; Masson-Delmotte, Valerie; Jouzel, Jean

2018-05-01

The oldest ice core records are obtained from the East Antarctic Plateau. Water isotopes are key proxies to reconstructing past climatic conditions over the ice sheet and at the evaporation source. The accuracy of climate reconstructions depends on knowledge of all processes affecting water vapour, precipitation and snow isotopic compositions. Fractionation processes are well understood and can be integrated in trajectory-based Rayleigh distillation and isotope-enabled climate models. However, a quantitative understanding of processes potentially altering snow isotopic composition after deposition is still missing. In low-accumulation sites, such as those found in East Antarctica, these poorly constrained processes are likely to play a significant role and limit the interpretability of an ice core's isotopic composition. By combining observations of isotopic composition in vapour, precipitation, surface snow and buried snow from Dome C, a deep ice core site on the East Antarctic Plateau, we found indications of a seasonal impact of metamorphism on the surface snow isotopic signal when compared to the initial precipitation. Particularly in summer, exchanges of water molecules between vapour and snow are driven by the diurnal sublimation-condensation cycles. Overall, we observe in between precipitation events modification of the surface snow isotopic composition. Using high-resolution water isotopic composition profiles from snow pits at five Antarctic sites with different accumulation rates, we identified common patterns which cannot be attributed to the seasonal variability of precipitation. These differences in the precipitation, surface snow and buried snow isotopic composition provide evidence of post-deposition processes affecting ice core records in low-accumulation areas.

Compound-specific isotopic analyses: a novel tool for reconstruction of ancient biogeochemical processes

NASA Technical Reports Server (NTRS)

Hayes, J. M.; Freeman, K. H.; Popp, B. N.; Hoham, C. H.

1990-01-01

Patterns of isotopic fractionation in biogeochemical processes are reviewed and it is suggested that isotopic fractionations will be small when substrates are large. If so, isotopic compositions of biomarkers will reflect those of their biosynthetic precursors. This prediction is tested by consideration of results of analyses of geoporphyrins and geolipids from the Greenhorn Formation (Cretaceous, Western Interior Seaway of North America) and the Messel Shale (Eocene, lacustrine, southern Germany). It is shown (i) that isotopic compositions of porphyrins that are related to a common source, but which have been altered structurally, cluster tightly and (ii) that isotopic differences between geolipids and porphyrins related to a common source are equal to those observed in modern biosynthetic products. Both of these observations are consistent with preservation of biologically controlled isotopic compositions during diagenesis. Isotopic compositions of individual compounds can thus be interpreted in terms of biogeochemical processes in ancient depositional environments. In the Cretaceous samples, isotopic compositions of n-alkanes are covariant with those of total organic carbon, while delta values for pristane and phytane are covariant with those of porphyrins. In this unit representing an open marine environment, the preserved acyclic polyisoprenoids apparently derive mainly from primary material, while the extractable, n-alkanes derive mainly from lower levels of the food chain. In the Messel Shale, isotopic compositions of individual biomarkers range from -20.9 to -73.4% vs PDB. Isotopic compositions of specific compounds can be interpreted in terms of origin from methylotrophic, chemautotrophic, and chemolithotrophic microorganisms as well as from primary producers that lived in the water column and sediments of this ancient lake.

Seasonality of Oxygen isotope composition in cow (Bos taurus) hair and its model interpretation

NASA Astrophysics Data System (ADS)

Chen, Guo; Schnyder, Hans; Auerswald, Karl

2017-04-01

Oxygen isotopes in animal and human tissues are expected to be good recorders of geographical origin and migration histories based on the isotopic relationship between hair oxygen and annual precipitation and the well-known spatial pattern of oxygen isotope composition in meteoric water. However, seasonal variation of oxygen isotope composition may diminish the origin information in the tissues. Here the seasonality of oxygen isotope composition in tail hair was investigated in a domestic suckler cow (Bos taurus) that underwent different ambient conditions, physiological states, and keeping and feeding strategies during five years. A detailed mechanistic model involving in ambient conditions, soil properties and animal physiology was built to explain this variation. The measured oxygen isotope composition in hair was significantly related (p<0.05) to the isotope composition in meteoric water in a regression analysis. Modelling suggested that this relation was only partly derived from the direct influence of feed moisture. Ambient conditions (temperature, moisture) did not only influence the isotopic signal of precipitation but also affected the animal itself (drinking water demand, transcutaneous vapor etc.). The clear temporal variation thus resulted from complex interactions with multiple influences. The twofold influence of ambient conditions via the feed and via the animal itself is advantageous for tracing the geographic origin because the oxygen isotope composition is then less influenced by variations in moisture uptake; however, it is unfavorable for indicating the production system, e.g. to distinguish between milk produced from fresh grass or from silage.

In situ Fenton reagent generated from TiO2/Cu2O composite film: a new way to utilize TiO2 under visible light irradiation.

PubMed

Zhang, Yong-Gang; Ma, Li-Li; Li, Jia-Lin; Yu, Ying

2007-09-01

TiO2/Cu2O composite is prepared by a simple electrochemical method and coated on glass matrix through a spraying method. The obtained composite is characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effect of TiO2/Cu2O composite films with different ratio of TiO2 and Cu2O on photodegradation of the dye methylene blue under visible light is investigated in detail. It is found that the photocatalytic activity of TiO2/Cu2O composite film with the presence of FeSO4 and EDTA is much higher than that for the similar system with only TiO2 and Cu2O film respectively. Without the presence of FeSO4 and EDTA, there is no degradation for methylene blue. The exploration of the optimized parameters for the degradation of methylene blue by using TiO2/Cu2O composite film as catalyst under visible light was also carried out. The most significant factor is the amount of Ti02 in the composite, and the second significant factor is the concentration of FeSO4. During the degradation of methylene blue under visible light, TiO2/Cu2O composite film generates H202, and Fenton regent is formed with Fe2+ and EDTA, which is detected in this study. The mechanism for the great improvement of photocatalytic activity of TiO2/Cu2O composite film under visible light is proposed by the valence band theory. Electrons excitated from TiO2/Cu2O composite under visible light are transferred from the conduction band of Cu2O to that of Ti02. The formed intermediate state of Ti 3+ ion is observed by X-ray photoelectron spectroscopy (XPS) on the TiO/Cu2O composite film. Additionally, the accumulated electrons in the conduction band of TiO2 are transferred to oxygen on the TiO2 surface for the formation of O2- or O2(2-), which combines with H+ to form H2O2. The evolved H202 with FeSO4 and EDTA forms Fenton reagentto degrade methylene blue. Compared to the traditional Fenton reagent, this new kind of in situ Fenton reagent generated from TiO2/Cu2O composite film does not need to supply H202. It is expected to be easily recycled, which may reduce second pollution and the cost of wastewater treatment. Moreover, this TiO/Cu2O composite film with FeSO4 and EDTA provides a new way to take advantage of TiO2 under visible light.

Zinc isotopes in sphalerite from base metal deposits in the Red Dog district, northern Alaska

USGS Publications Warehouse

Kelley, K.D.; Wilkinson, J.J.; Chapman, J.B.; Crowther, H.L.; Weiss, D.J.

2009-01-01

Analyses of sphalerite samples from shale-hosted massive sulfide and stratigraphically underlying vein breccia deposits in the Red Dog district in northern Alaska show a range ??66Zn values from zero to 0.60 per mil. The lowest values are observed in the vein breccia deposits, and the stratigraphically overlying (but structurally displaced) shale-hosted massive sulfide deposits show a systematic trend of increasing ??66Zn values from south to north (Main-Aqqaluk-Paalaaq-Anarraaq). The ??66Zn values are inversely correlated with sphalerite Fe/Mn ratio and also tend to be higher in low Cu sphalerite, consistent with precipitation of lower ??66Zn sphalerite closer to the principal hydrothermal fluid conduits. The most likely control on isotopic variation is Rayleigh fractionation during sulfide precipitation, with lighter zinc isotopes preferentially incorporated in the earliest sphalerite to precipitate from ore fluids at deeper levels (vein breccias) and close to the principal fluid conduits in the orebodies, followed by precipitation of sulfides with higher ??66Zn values in shallower and/or more distal parts of the flow path. There is no systematic variation among the paragenetic stages of sphalerite from a single deposit, suggesting an isotopically homogeneous zinc source and consistent transport-deposition conditions and/or dissolution-reprecipitation of earlier sphalerite without significant fractionation. Decoupled Zn and S isotope compositions are best explained by mixing of separate metal- and sulfur-bearing fluids at the depositional site. The results confirm that Zn isotopes may be a useful tracer for distinguishing between the central and distal parts of large hydrothermal systems as previously suggested and could therefore be of use in exploration. ?? 2009 by Economic Geology.

High strength-high conductivity Cu-Fe composites produced by powder compaction/mechanical reduction

DOEpatents

Verhoeven, J.D.; Spitzig, W.A.; Gibson, E.D.; Anderson, I.E.

1991-08-27

A particulate mixture of Cu and Fe is compacted and mechanically reduced to form an ''in-situ'' Cu-Fe composite having high strength and high conductivity. Compaction and mechanical reduction of the particulate mixture are carried out at a temperature and time at temperature selected to avoid dissolution of Fe into the Cu matrix particulates to a harmful extent that substantially degrades the conductivity of the Cu-Fe composite. 5 figures.

Nitrate removal by Fe0/Pd/Cu nano-composite in groundwater.

PubMed

Liu, Hongyuan; Guo, Min; Zhang, Yan

2014-01-01

Nitrate pollution in groundwater shows a great threat to the safety of drinking water. Chemical reduction by zero-valent iron is being considered as a promising technique for nitrate removal from contaminated groundwater. In this paper, Fe0/Pd/Cu nano-composites were prepared by the liquid-phase reduction method, and batch experiments of nitrate reduction by the prepared Fe0/Pd/Cu nano-composites under various operating conditions were carried out. It has been found that nano-Fe0/Pd/Cu composites processed dual functions: catalytic reduction and chemical reduction. The introduction of Pd and Cu not only improved nitrate removal rate, but also reduced the generation of ammonia. Nitrate removal rate was affected by the amount of Fe0/Pd/Cu, initial nitrate concentration, solution pH, dissolved oxygen (DO), reaction temperature, the presence of anions, and organic pollutant. Moreover, nitrate reduction by Fe0/Pd/Cu composites followed the pseudo-first-order reaction kinetics. The removal rate of nitrate and total nitrogen were about 85% and 40.8%, respectively, under the reaction condition of Fe-6.0%Pd-3.0%Cu amount of 0.25 g/L, pH value of 7.1, DO of 0.42 mg/L, and initial nitrate concentration of 100 mg/L. Compared with the previous studies with Fe0 alone or Fe-Cu, nano-Fe-6%Pd-3%Cu composites showed a better selectivity to N2.

Magnesium isotopic composition of the mantle

NASA Astrophysics Data System (ADS)

Teng, F.; Li, W.; Ke, S.; Marty, B.; Huang, S.; Dauphas, N.; Wu, F.; Helz, R. L.

2009-12-01

Studies of Mg isotopic composition of the Earth not only are important for understanding its geochemistry but also can shed light on the accretion history of the Earth as well as the evolution of the Earth-Moon system. However, to date, the Mg isotopic composition of the Earth is still poorly constrained and highly debated. There is uncertainty in the magnitude of Mg isotope fractionation at mantle temperatures and whether the Earth has a chondritic Mg isotopic composition or not. To constrain further the Mg isotopic composition of the mantle and investigate the behavior of Mg isotopes during igneous differentiation, we report >200 high-precision (δ26Mg < 0.1‰, 2SD) analyses of Mg isotopes on 1) global mid-ocean ridge basalts covering major ridge segments of the world and spanning a broad range in latitudes, chemical and radiogenic isotopic compositions; 2) ocean island basalts from Hawaiian (Koolau, Kilauea and Loihi) and French Polynesian volcanoes (Society island and Cook Austral chain); 3) olivine grains from Hawaiian volcanoes (Kilauea, Koolau and Loihi) and 4) peridotite xenoliths from Australia, China, France, Tanzania and USA. Global oceanic basalts and peridotite xenoliths have a limited (<0.2 ‰) variation in Mg isotopic composition, with an average δ26Mg = -0.25 relative to DSM3. Olivines from Hawaiian lavas have δ26Mg ranging from -0.43 to +0.03, with most having compositions identical to basalts and peridotites. Therefore, the mantle’s δ26Mg value is estimated to be ~ -0.25 ± 0.1 (2SD), different from that reported by Wiechert and Halliday (2007; δ26Mg = ~ 0) but similar to more recent studies (δ26Mg = -0.27 to -0.33) (Teng et al. 2007; Handler et al. 2009; Yang et al., 2009). Moreover, we suggest the Earth, as represented by the mantle, has a Mg isotopic composition similar to chondrites (δ26Mg = ~-0.33). The need for a model such as that of Wiechert and Halliday (2007) that involves sorting of chondrules and calcium-aluminum-rich inclusions in the proto planetary disc is thus not required to explain the Mg isotopic composition of the Earth.

ISOTOPE CONVERSION DEVICE

DOEpatents

Wigner, E.P.; Young, G.J.; Ohlinger, L.A.

1957-12-01

This patent relates to nuclear reactors of tbe type utilizing a liquid fuel and designed to convert a non-thermally fissionable isotope to a thermally fissionable isotope by neutron absorption. A tank containing a reactive composition of a thermally fissionable isotope dispersed in a liquid moderator is disposed within an outer tank containing a slurry of a non-thermally fissionable isotope convertible to a thermally fissionable isotope by neutron absorption. A control rod is used to control the chain reaction in the reactive composition and means are provided for circulating and cooling the reactive composition and slurry in separate circuits.

MAST - A mass spectrometer telescope for studies of the isotopic composition of solar, anomalous, and galactic cosmic ray nuclei

NASA Technical Reports Server (NTRS)

Cook, Walter R.; Cummings, Alan C.; Cummings, Jay R.; Garrard, Thomas L.; Kecman, Branislav; Mewaldt, Richard A.; Selesnick, Richard S.; Stone, Edward C.; Von Rosenvinge, T. T.

1993-01-01

The Mass Spectrometer Telescope (MAST) on SAMPEX is designed to provide high resolution measurements of the isotopic composition of energetic nuclei from He to Ni (Z = 2 to 28) over the energy range from about 10 to several hundred MeV/nuc. During large solar flares MAST will measure the isotopic abundances of solar energetic particles to determine directly the composition of the solar corona, while during solar quiet times MAST will study the isotopic composition of galactic cosmic rays. In addition, MAST will measure the isotopic composition of both interplanetary and trapped fluxes of anomalous cosmic rays, believed to be a sample of the nearby interstellar medium.

Long-term data set analysis of stable isotopic composition in German rivers

NASA Astrophysics Data System (ADS)

Reckerth, Anne; Stichler, Willibald; Schmidt, Axel; Stumpp, Christine

2017-09-01

Stable isotopes oxygen-18 (18O) and deuterium (2H) are commonly used to investigate hydrological processes in catchments. However, only a few isotope studies have been conducted on a large scale and rarely over long time periods. The objective of this study was to identify the spatial and seasonal variability of isotopic composition in river water and how it is affected by geographical and hydrological factors. The stable isotopic composition of river water has been measured in nine large river catchments in Germany for a time period of 12 years or 26 years. We conducted time series and correlation analyses to identify spatial and temporal patterns of the isotopic composition in the rivers. Further, we compared it to isotopic composition in local precipitation and catchments characteristics. In the majority of the rivers, the spatial and temporal patterns of precipitation were directly reflected in river water. The isotopic signals of the river water were time shifted and show attenuated amplitudes. Further deviations from isotopic compositions in local precipitation were observed in catchments with complex flow systems. These deviations were attributed to catchment processes and influences like evaporation, damming and storage. The seasonality of the isotopic composition was mainly determined by the discharge regimes of the rivers. We found correlations between isotopic long-term averages and catchment altitude as well as latitude and longitude, resulting in a northwest-southeast gradient. Furthermore, it was shown that long-term averages of d-excess were inversely related to flow length and catchment size, which indicates that evaporation enrichment has an impact on the isotopic composition even in catchments of humid climates. This study showed that isotopic composition in rivers can serve as a proxy for the local precipitation and can be utilized as an indicator for hydrological processes even in large river basins. In future, such long time series will help to also understand the impact of changes in the hydrological cycle on the larger scales. They can also be used for calibration and validation of flow and transport models at catchment and sub-catchment scale.

Biogeochemical cycling in an organic-rich coastal marine basin. 8. A sulfur isotopic budget balanced by differential diffusion across the sediment-water interface

USGS Publications Warehouse

Chanton, J.P.; Martens, C.S.; Goldhaber, M.B.

1987-01-01

The sulfur isotopic composition of the sulfur fluxes occurring in the anoxic marine sediments of Cape Lookout Bight, N.C., U.S.A., was determined, and the result of isotopic mass balance was obtained via the differential diffusion model. Seasonal pore water sulfate ??34S measurements yielded a calculated sulfate input of 0.6%.. Sulfate transported into the sediments via diffusion appeared to be enriched in the lighter isotope because its concentration gradient was steeper, due to the increase in the measured isotopic composition of sulfate with depth. Similarly, the back diffusion of dissolved sulfide towards the sediment-water interface appeared enriched in the heavier isotope. The isotopic composition of this flux was calculated from measurements of the ??34S of dissolved sulfide and was determined to be 15.9%.. The isotopic composition of buried sulfide was determined to be -5.2%. and the detrital sulfur input was estimated to be -6.2%.. An isotope mass balance equation based upon the fluxes at the sediment-water interface successfully predicted the isotopic composition of the buried sulfur flux within 0.5%., thus confirming that isotopes diffuse in response to their individual concentration gradients. ?? 1987.

Determining metal assimilation efficiency in aquatic invertebrates using enriched stable metal isotope tracers

USGS Publications Warehouse

Croteau, M.-N.; Luoma, S.N.; Pellet, B.

2007-01-01

We employ a novel approach that combines pulse-chase feeding and multi-labelled stable isotopes to determine gut passage time (GPT), gut retention time (GRT), food ingestion rate (IR) and assimilation efficiency (AE) of three trace elements for a freshwater gastropod. Lettuce isotopically enriched in 53Cr, 65Cu and 106Cd was fed for 2 h to Lymnaea stagnalis. The release of tracers in feces and water was monitored for 48 h, during which unlabelled lettuce was provided ad libidum. The first defecation of 53Cr occurred after 5 h of depuration (GPT), whereas 90% of the ingested 53Cr was recovered in the feces after 22.5 h of depuration (GRT). 53Chromium was not significantly accumulated in the soft tissues upon exposure. In contrast, 65Cu and 106Cd assimilation was detectable for most experimental snails, i.e., 65/63Cu and 106/114Cd ratios in exposed snails were higher than those for controls. Food IR during the labelled feeding phase was 0.16 ?? 0.07 g g-1 d-1. IR was inferred from the amount of 53Cr egested in the feces during depuration and the concentration of 53Cr in the labelled lettuce. Assimilation efficiencies (??95% CI) determined using mass balance calculations were 84 ?? 4% for Cu and 85 ?? 3% for Cd. The ratio method yields similar AE estimates. Expanding the application of this novel stable isotope tracer technique to other metals in a wide variety of species will provide unique opportunities to evaluate the interplay between digestive processes and dietary influx of metals. Understanding the biological processes that modulate dietborne metal uptake is crucial to assess the toxicity of dietborne metals. ?? 2007 Elsevier B.V. All rights reserved.

Molybdenum Isotopic Composition of Iron Meteorites, Chondrites and Refractory Inclusions

NASA Technical Reports Server (NTRS)

Becker, H.; Walker, R. J.

2003-01-01

Recent Mo isotopic studies of meteorites reported evidence for differences in isotopic compositions for whole rocks of some primitive and differentiated meteorites relative to terrestrial materials. Enrichments of r- and p-process isotopes of up to 3-4 units (e unit = parts in 10(exp 4) over s-process dominated isotopes are the most prominent features. Certain types of presolar grains show large enrichments in s-process isotopes, however, it was concluded on grounds of mass balance that incomplete digestion of such grains cannot explain the enrichments of r- and p-process isotopes in whole rocks of primitive chondrites. If the reported variability in r- and p-process isotope enrichments reflects the true isotopic characteristics of the whole rocks, the implications are quite profound. It would suggest the presence of large scale Mo isotopic heterogeneity within the solar accretion disk with likely collateral effects for other elements. However, such effects were not found for Ru isotopes, nor for Zr isotopes. Another recent Mo isotopic study by multi collector ICP-MS could not confirm the reported deviations in Allende, Murchison or iron meteorites. Here, we present new results for the Mo isotopic composition of iron meteorites, chondrites and CAIs obtained by negative thermal ionization mass spectrometry (NTIMS). We discuss analytical aspects and the homogeneity of Mo isotopic compositions in solar system materials.

Synthesis of Cu-W nanocomposite by high-energy ball milling.

PubMed

Venugopal, T; Rao, K Prasad; Murty, B S

2007-07-01

The Cu-W bulk nanocomposites of different compositions were successfully synthesized by high-energy ball milling of elemental powders. The nanocrystalline nature of the Cu-W composite powder is confirmed by X-ray diffraction analysis, transmission electron microscopy, and atomic force microscopy. The Cu-W nanocomposite powder could be sintered at 300-400 degrees C below the sintering temperature of the un-milled Cu-W powders. The Cu-W nanocomposites showed superior densification and hardness than that of un-milled Cu-W composites. The nanocomposites also have three times higher hardness to resistivity ratio in comparison to Oxygen free high conductivity copper.

Geochronology and geochemistry of the Badaguan porphyry Cu-Mo deposit in Derbugan metallogenic belt of the NE China, and their geological significances

NASA Astrophysics Data System (ADS)

Gao, Bingyu; Zhang, Lianchang; Jin, Xindi; Li, Wenjun; Chen, Zhiguang; Zhu, Mingtian

2016-03-01

The Badaguan porphyry Cu-Mo deposit belongs to the Derbugan metallogenic belt, which is located in the Ergun block, NE China. In the mining area, the Cu-Mo mineralization mainly occurs in quartz diorite porphyry and is hosted within silicified-sericitized and sericite alteration zone. Geochemical results of the host porphyry is characterized by high SiO2, high Al2O3, low MgO, weak positive Eu anomalies and clearly HREE depletion, high Sr, low Y and low Yb, similar to those of adakite. The Sr-Nd isotopic composition of the host porphyry displays an initial (87Sr/86Sr)i ratio of 0.7036-0.7055 and positive Nd( t) values of +0.1 to +0.6, which are similar to the OIB, reflecting the source of the host porphyry may derive from subducted ocean slab, and the new lower crust also had some contribution to the magma sources. The SIMS zircon U-Pb age from the host porphyry is 229 ± 2 Ma. The Re-Os isochron age for the molybdenite in the deposit is 225 ± 2 Ma closed to zircon U-Pb age of the host porphyry, indicating that Cu-Mo mineralization event occurred in Triassic. Combining the geology-geochemistry of the host porphyry and the regional tectonic evolution, we infer that the subduction processes of Mongol-Okhotsk oceanic slab under the Ergun block led to the formation of the Badaguan porphyry Cu-Mo deposit during the Triassic.

Production of .sup.64 Cu and other radionuclides using a charged-particle accelerator

DOEpatents

Welch, Michael J.; McCarthy, Deborah W.; Shefer, Ruth E.; Klinkowstein, Robert E.

2000-01-01

Radionuclides are produced according to the present invention at commercially significant yields and at specific activities which are suitable for use in radiodiagnostic agents such as PET imaging agents and radiotherapeutic agents and/or compositions. In the method and system of the present invention, a solid target having an isotopically enriched target layer electroplated on an inert substrate is positioned in a specially designed target holder and irradiated with a charged-particle beam. The beam is preferably generated using an accelerator such as a biomedical cyclotron at energies ranging from about 5 MeV to about 25 MeV. The target is preferably directly irradiated, without an intervening attenuating foil, and with the charged particle beam impinging an area which substantially matches the target area. The irradiated target is remotely and automatically transferred from the target holder, preferably without transferring any target holder subassemblies, to a conveyance system which is preferably a pneumatic or hydraulic conveyance system, and then further transferred to an automated separation system. The system is effective for processing a single target or a plurality of targets. After separation, the unreacted target material can be recycled for preparation of other targets. In a preferred application of the invention, a biomedical cyclotron has been used to produce over 500 mCi of .sup.64 Cu having a specific activity of over 300 mCi/.mu.g Cu according to the reaction .sup.64 Ni(p,n).sup.64 Cu. These results indicate that accelerator-produced .sup.64 Cu is suitable for radiopharmaceutical diagnostic and therapeutic applications.

High Dielectric Constants of Composites of Fiber-Like Copper Phthalocyanine-Coated Graphene Oxide Embedded in Poly(arylene Ether Nitriles)

NASA Astrophysics Data System (ADS)

Li, Jingwei; Pu, Zejun; Wang, Zicheng; Long, Ya; Jia, Kun; Liu, Xiaobo

2015-07-01

The surfaces of graphene oxide (GO) sheets were coated with fiber-like copper phthalocyanine (CuPc) by use of a solvothermal process. The product, GO@ CuPc, was used as a filler in high-performance poly(arylene ether nitrile) (PEN) composites. Films of the composites had high thermal stability, and glass-transition temperatures in the range 170-182°C. Thermogravimetric analysis revealed their initial decomposition temperatures were in the range 470-483°C. Scanning electron microscopy showed that dispersion of GO@ CuPc in PEN was much better than that of unmodified GO; this can be attributed to relatively strong interaction between GO@CuPc and the PEN matrix. All the composite films were highly flexible and had enhanced mechanical properties. Tensile strengths of the composites were as high as 89 MPa in the presence of 1 wt.% GO@CuPc, an increase of 20% compared with pure PEN film. Dielectric constants of the composite films were as high as 52 at 100 Hz when the GO@CuPc content was 5%. Because of these excellent mechanical and dielectric properties, PEN/GO@CuPc composites have much potential for use as film capacitors.

Novel Preparation of Nano-Composite CuO-Cr2O3 Using Ctab-Template Method and Efficient for Hydrogenation of Biomass-Derived Furfural

NASA Astrophysics Data System (ADS)

Yan, Kai; Wu, Xu; An, Xia; Xie, Xianmei

2013-02-01

A simple route to fabricate nano-composite oxides CuO-Cr2O3 using hexadecyltrimethylammonium bromide (CTAB)-templated Cu-Cr hydrotalcite as the precursor is presented. This novel method is based on CTAB-templating effect for mesostructure directing and using the cheap metal nitrate, followed by removal of CTAB. It was indicated that the nano-composite CuO-Cr2O3 was formed during the removal of CTAB. X-ray diffraction (XRD) and transitional electronic microscopy (TEM) revealed nice nano-composite oxides CuO-Cr2O3 were formed with high crystallinity. N2 adsorption and desorption indicated that a high surface area of 170.5 m2/g with a pore size of 2.7 nm of the nano-composite CuO-Cr2O3 was facilely resulted. The as-synthesized nano-composite oxides CuO-Cr2O3 display good catalytic activities for hydrogenation of furfural to furfuryl alcohol, whereas 86% selectivity was achieved at 75% conversion of furfural.

Formation of NO + and its possible roles during the selective catalytic reduction of NOx with NH 3 on Cu-CHA catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Hai-Ying; Kollar, Marton; Wei, Zhehao

The catalytic activities of small-pore Cu-CHA and large-pore Cu-BEA catalysts for the selective catalytic reduction of NO with NH 3 were measured at a very high flow rate. Cu-CHA clearly exhibited much higher intrinsic SCR activity and lower N 2O selectivity. In situ DRIFT spectra were recorded during the adsorption and desorption following NO and (NO+O 2) exposure to fully oxidized samples in a flow cell. The results are in agreement with what we have reported previously based on in situ transmission IR studies of partially reduced samples. Both suggest that different SCR reaction pathways might exist on these twomore » catalysts and that NO + could be an important reaction intermediate for Cu-CHA. Detailed IR studies with various isotopically labeled gas mixtures of (NO+O 2), ( 15NO+O 2), (NO+ 18O 2) and ( 15N 18O+O 2) were conducted to understand the origin of the surface adsorption complexes on Cu-CHA. Formation of NO + was not the consequence of a simple charge transfer reaction, NO+Cu 2+=NO+ + Cu +. Instead, O 2 was found to be essential in changing the oxidation state of N from +2 to +3 although it did not participate in new N$-$O bond formation. In conclusion, the majority of the adsorbed NO + maintained its isotopic origin of the feed gas.« less

Formation of NO + and its possible roles during the selective catalytic reduction of NOx with NH 3 on Cu-CHA catalysts

DOE PAGES

Chen, Hai-Ying; Kollar, Marton; Wei, Zhehao; ...

2017-12-21

The catalytic activities of small-pore Cu-CHA and large-pore Cu-BEA catalysts for the selective catalytic reduction of NO with NH 3 were measured at a very high flow rate. Cu-CHA clearly exhibited much higher intrinsic SCR activity and lower N 2O selectivity. In situ DRIFT spectra were recorded during the adsorption and desorption following NO and (NO+O 2) exposure to fully oxidized samples in a flow cell. The results are in agreement with what we have reported previously based on in situ transmission IR studies of partially reduced samples. Both suggest that different SCR reaction pathways might exist on these twomore » catalysts and that NO + could be an important reaction intermediate for Cu-CHA. Detailed IR studies with various isotopically labeled gas mixtures of (NO+O 2), ( 15NO+O 2), (NO+ 18O 2) and ( 15N 18O+O 2) were conducted to understand the origin of the surface adsorption complexes on Cu-CHA. Formation of NO + was not the consequence of a simple charge transfer reaction, NO+Cu 2+=NO+ + Cu +. Instead, O 2 was found to be essential in changing the oxidation state of N from +2 to +3 although it did not participate in new N$-$O bond formation. In conclusion, the majority of the adsorbed NO + maintained its isotopic origin of the feed gas.« less

Do Hf isotopes in magmatic zircons represent those of their host rocks?

NASA Astrophysics Data System (ADS)

Wang, Di; Wang, Xiao-Lei; Cai, Yue; Goldstein, Steven L.; Yang, Tao

2018-04-01

Lu-Hf isotopic system in zircon is a powerful and widely used geochemical tracer in studying petrogenesis of magmatic rocks and crustal evolution, assuming that zircon Hf isotopes can represent initial Hf isotopes of their parental whole rock. However, this assumption may not always be valid. Disequilibrium partial melting of continental crust would preferentially melt out non-zircon minerals with high time-integrated Lu/Hf ratios and generate partial melts with Hf isotope compositions that are more radiogenic than those of its magma source. Dissolution experiments (with hotplate, bomb and sintering procedures) of zircon-bearing samples demonstrate this disequilibrium effect where partial dissolution yielded variable and more radiogenic Hf isotope compositions than fully dissolved samples. A case study from the Neoproterozoic Jiuling batholith in southern China shows that about half of the investigated samples show decoupled Hf isotopes between zircons and the bulk rocks. This decoupling could reflect complex and prolonged magmatic processes, such as crustal assimilation, magma mixing, and disequilibrium melting, which are consistent with the wide temperature spectrum from ∼630 °C to ∼900 °C by Ti-in-zircon thermometer. We suggest that magmatic zircons may only record the Hf isotopic composition of their surrounding melt during crystallization and it is uncertain whether their Hf isotopic compositions can represent the primary Hf isotopic compositions of the bulk magmas. In this regard, using zircon Hf isotopic compositions to trace crustal evolution may be biased since most of these could be originally from disequilibrium partial melts.

Oxygen Isotope Measurements of a Rare Murchison Type A CAI and Its Rim

NASA Technical Reports Server (NTRS)

Matzel, J. E. P.; Simon, J. I.; Hutcheon, I. D.; Jacobsen, B.; Simon, S. B.; Grossman, L.

2013-01-01

Ca-, Al-rich inclusions (CAIs) from CV chondrites commonly show oxygen isotope heterogeneity among different mineral phases within individual inclusions reflecting the complex history of CAIs in both the solar nebula and/or parent bodies. The degree of isotopic exchange is typically mineral-specific, yielding O-16-rich spinel, hibonite and pyroxene and O-16-depleted melilite and anorthite. Recent work demonstrated large and systematic variations in oxygen isotope composition within the margin and Wark-Lovering rim of an Allende Type A CAI. These variations suggest that some CV CAIs formed from several oxygen reservoirs and may reflect transport between distinct regions of the solar nebula or varying gas composition near the proto-Sun. Oxygen isotope compositions of CAIs from other, less-altered chondrites show less intra-CAI variability and 16O-rich compositions. The record of intra-CAI oxygen isotope variability in CM chondrites, which commonly show evidence for low-temperature aqueous alteration, is less clear, in part because the most common CAIs found in CM chondrites are mineralogically simple (hibonite +/- spinel or spinel +/- pyroxene) and are composed of minerals less susceptible to O-isotopic exchange. No measurements of the oxygen isotope compositions of rims on CAIs in CM chondrites have been reported. Here, we present oxygen isotope data from a rare, Type A CAI from the Murchison meteorite, MUM-1. The data were collected from melilite, hibonite, perovskite and spinel in a traverse into the interior of the CAI and from pyroxene, melilite, anorthite, and spinel in the Wark-Lovering rim. Our objectives were to (1) document any evidence for intra-CAI oxygen isotope variability; (2) determine the isotopic composition of the rim minerals and compare their composition(s) to the CAI interior; and (3) compare the MUM-1 data to oxygen isotope zoning profiles measured from CAIs in other chondrites.

Surfactant-free electrodeposition of reduced graphene oxide/copper composite coatings with enhanced wear resistance

NASA Astrophysics Data System (ADS)

Mai, Y. J.; Zhou, M. P.; Ling, H. J.; Chen, F. X.; Lian, W. Q.; Jie, X. H.

2018-03-01

How to uniformly disperse graphene sheets into the electrolyte is one of the main challenges to synthesize graphene enhanced nanocomposites by electrodeposition. A surfactant-free colloidal solution comprised of copper (II)-ethylene diamine tetra acetic acid ([CuIIEDTA]2-) complexes and graphene oxide (GO) sheets is proposed to electrodeposit reduced graphene oxide/copper (RGO/Cu) composite coatings. Anionic [CuIIEDTA]2- complexes stably coexist with negatively charged GO sheets due to the electrostatic repulsion between them, facilitating the electrochemical reduction and uniform dispersion of GO sheets into the copper matrix. The RGO/Cu composite coatings are well characterized by XRD, Raman, SEM and XPS. Their tribological behavior as a function of RGO content in composite coatings and normal loads are investigated. Also the chemical composition and topography of the wear tracks for the composite coatings are analyzed to deduce the lubricating and anti-wear mechanism of RGO/Cu composite coatings.

Incorporation of Copper Enhances the Anti-Ageing Property of Flame-Sprayed High-Density Polyethylene Coatings

NASA Astrophysics Data System (ADS)

Jia, Zhengmei; Huang, Jing; Gong, Yongfeng; Jin, Peipeng; Suo, Xinkun; Li, Hua

2017-02-01

High-density polyethylene (HDPE)-copper (Cu) composite coatings were prepared through depositing HDPE-Cu core-shell particles by flame spraying. The HDPE-Cu composite coatings and the HDPE coatings were aged in xenon lamp ageing testing chamber. The variations of chemical compositions and surface morphology of the coatings before and after the ageing testing were analyzed using infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry and ultraviolet-visible spectrophotometer. Results show that there is no chemical composition variation in the HDPE-Cu coatings. Cracks were found on the surfaces of the HDPE coatings, while the HDPE-Cu coating shows almost intact surface morphology. These results suggest that the HDPE-Cu coatings present better anti-ageing performances than the HDPE coatings. Further assessment of the function of Cu shells on the anti-ageing property reveals that Cu shells not only enhanced the absorption of the coatings to ultraviolet, but also increased their reflectivity to visible light. Additionally, the Cu shells enhanced the decomposition temperature and thermal stability of HDPE in the composite coatings. These results give bright insight into potential anti-ageing applications of the polymer-based structures.

Magnesium isotopic evidence for chemical disequilibrium among cumulus minerals in layered mafic intrusion

NASA Astrophysics Data System (ADS)

Chen, Lie-Meng; Teng, Fang-Zhen; Song, Xie-Yan; Hu, Rui-Zhong; Yu, Song-Yue; Zhu, Dan; Kang, Jian

2018-04-01

Magnesium isotopic compositions of olivine, clinopyroxene, and ilmenite from the Baima intrusion, SW China, for the first time, are investigated to constrain the magnitude and mechanisms of Mg isotope fractionation among cumulus minerals in layered mafic intrusions and to evaluate their geological implications. Olivine and clinopyroxene have limited Mg isotope variations, with δ26Mg ranging from -0.33 to +0.05‰ and from -0.29 to -0.13‰, respectively, similar to those of mantle xenolithic peridotites. By contrast, ilmenites display extremely large Mg isotopic variation, with δ26Mg ranging from -0.50 to +1.90‰. The large inter-mineral fractionations of Mg isotopes between ilmenite and silicates may reflect both equilibrium and kinetic processes. A few ilmenites have lighter Mg isotopic compositions than coexisting silicates and contain high MgO contents without compositional zoning, indicating equilibrium fractionation. The implication is that the light Mg isotopic compositions of lunar high-Ti basalts may result from an isotopically light source enriched in cumulate ilmenites. On the other hand, most ilmenites have heavy Mg isotopic compositions, coupled with high MgO concentration and chemical zoning, which can be quantitatively modeled by kinetic Mg isotope fractionations induced by subsolidus Mg-Fe exchange between ilmenite and ferromagnesian silicates during the cooling of the Baima intrusion. The extensive occurrence of kinetic Mg isotope fractionation in ilmenites implies the possibility of widespread compositional disequilibrium among igneous minerals in magma chambers. Consequently, disequilibrium effects need to be considered in studies of basaltic magma evolution, magma chamber processes, and magmatic Fe-Ti oxide ore genesis.

The thermo-mechanical behaviour of W-Cu metal matrix composites for fusion heat sink applications: The influence of the Cu content

NASA Astrophysics Data System (ADS)

Tejado, E.; Müller, A. v.; You, J.-H.; Pastor, J. Y.

2018-01-01

Copper and its alloys are used as heat sink materials for next generation fusion devices and will be joined to tungsten as an armour material. However, the joint of W and Cu experiences high thermal stresses when exposed to high heat loads so an interlayer material could effectively ensure the lifetime of the component by reducing the thermal mismatch. Many researchers have published results on the production of W-Cu composites aiming attention at its thermal conductivity; nevertheless, the mechanical performance of these composites remains poor. This paper reports the characterization of the thermo-mechanical behaviour of W-Cu composites produced via a liquid Cu melt infiltration of porous W preform. This technique was applied to produce composites with 15, 30 and 40 wt% Cu. The microstructure, thermal properties, and mechanical performance were investigated and measured from RT to 800 °C. The results demonstrated that high densification and superior mechanical properties can indeed be achieved via this manufacturing route. The mechanical properties (elastic modulus, fracture toughness, and strength) of the composites show a certain dependency on the Cu content; fracture mode shifts from the dominantly brittle fracture of W particles with constrained deformation of the Cu phase at low Cu content to the predominance of the ductile fracture of Cu when its ratio is higher. Though strong degradation is observed at 800 °C, the mechanical properties at operational temperatures, i.e. below 350 °C, remain rather high-even better than W/Cu materials reported previously. In addition, we demonstrated that the elastic modulus, and therefore the coefficient of thermal expansion, can be tailored via control of the W skeleton's porosity. As a result, the W-Cu composites presented here would successfully drive away heat produced in the fusion chamber avoiding the mismatch between materials while contributing to the structural support of the system.

Synthesis of Hierarchical Nanoporous Microstructures via the Kirkendall Effect in Chemical Reduction Process

NASA Astrophysics Data System (ADS)

Gao, Ling; Pang, Chao; He, Dafang; Shen, Liming; Gupta, Arunava; Bao, Ningzhong

2015-11-01

A series of novel hierarchical nanoporous microstructures have been synthesized through one-step chemical reduction of micron size Cu2O and Co3O4 particles. By controlling the reduction time, non-porous Cu2O microcubes sequentially transform to nanoporous Cu/Cu2O/Cu dented cubic composites and hollow eightling-like Cu microparticles. The mechanism involved in the complex structural evolution is explained based on oxygen diffusion and Kirkendall effect. The nanoporous Cu/Cu2O/Cu dented cubic composites exhibit superior electrochemical performance as compared to solid Cu2O microcubes. The reduction of nonporous Co3O4 also exhibits a uniform sequential reduction process from nonporous Co3O4 to porous Co3O4/CoO composites, porous CoO, porous CoO/Co composites, and porous foam-like Co particles. Nanoscale channels originate from the particle surface and eventually develop inside the entire product, resulting in porous foam-like Co microparticles. The Kirkendall effect is believed to facilitate the formation of porous structures in both processes.

Negative permittivity and permeability spectra of Cu/yttrium iron garnet hybrid granular composite materials in the microwave frequency range

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsutaoka, Takanori, E-mail: tsutaok@hiroshima-u.ac.jp; Fukuyama, Koki; Kinoshita, Hideaki

2013-12-23

The relative complex permittivity and permeability spectra of the coagulated copper and yttrium iron garnet (Cu/YIG) hybrid granular composite materials have been studied in the microwave range. The insulator to metal transition was observed at the percolation threshold of Cu particle content (φ{sub Cu} = 16.0 vol. %) in the electrical conductivity. In the percolation threshold, the low frequency plasmonic state caused by the metallic Cu particle networks was observed. The percolated Cu/YIG granular composites show simultaneous negative permittivity and permeability spectra under external magnetic fields.

Preparation of Advanced CuO Nanowires/Functionalized Graphene Composite Anode Material for Lithium Ion Batteries

PubMed Central

Zhang, Jin; Wang, Beibei; Zhou, Jiachen; Xia, Ruoyu; Chu, Yingli; Huang, Jia

2017-01-01

The copper oxide (CuO) nanowires/functionalized graphene (f-graphene) composite material was successfully composed by a one-pot synthesis method. The f-graphene synthesized through the Birch reduction chemistry method was modified with functional group “–(CH2)5COOH”, and the CuO nanowires (NWs) were well dispersed in the f-graphene sheets. When used as anode materials in lithium-ion batteries, the composite exhibited good cyclic stability and decent specific capacity of 677 mA·h·g−1 after 50 cycles. CuO NWs can enhance the lithium-ion storage of the composites while the f-graphene effectively resists the volume expansion of the CuO NWs during the galvanostatic charge/discharge cyclic process, and provide a conductive paths for charge transportation. The good electrochemical performance of the synthesized CuO/f-graphene composite suggests great potential of the composite materials for lithium-ion batteries anodes. PMID:28772432

Tracing subducted crustal materials in the mantle by using magnesium isotopes

NASA Astrophysics Data System (ADS)

Teng, F. Z.

2016-12-01

Recent studies show that some continental basalt, mantle-metasomatised peridotite and cratonic eclogite have heterogeneous Mg isotopic compositions. These isotopically distinct Mg isotopic compositions have been explained by the incorporation of subducted materials in their mantle sources though the detailed mechanisms are still not well understood. In particular, how Mg-poor crustal materials can modify Mg isotopic systematics of Mg-rich mantle is unknown. Subduction zones are the most efficient sites for crust and mantle interactions, hence should be where the most prominent Mg isotopic variation occurs. However, to date, little is known on Mg isotope systematics in the subduction factory. Here I first review and report new Mg isotopic data for arc lava, subarc peridotite and the subducted slab (marine sediment, altered basalt and abyssal peridotite), then use them to constrain the origins of mantle Mg isotopic heterogeneity and lay the foundation for using Mg isotopes as new tools for tracing crust-mantle interactions. The main conclusions are 1) fluid-rock interactions can modify Mg isotopic systematics of abyssal peridotites; 2) island arc lavas have non-MORB Mg isotopic compositions, reflecting distinct surbarc mantle Mg isotopic signature; 3) continental arcs have non-MORB Mg isotopic compositions, likely resulting from crustal contamination and 4) the isotopically heterogeneous continental basalts are mainly produced by mixing of isotopically distinct magmas instead of being partial melting products of metasomatised mantle peridotites.

Significant enhancement in volumetric and gravimetric capacitance of Cu-TiO2/PPY composite for supercapacitor application

NASA Astrophysics Data System (ADS)

Purty, B.; Choudhary, R. B.

2018-04-01

Copper doped titanium dioxide-polypyrrole (Cu-TiO2/PPY) composite was successfully synthesized via chemical oxidative in-situ polymerization process. The structural and morphological properties of Cu-TiO2/PPY composite were investigated using X-ray diffractometer (XRD), field emission electron microscopy (FESEM) and transmission electron microscopy(TEM) techniques. The electrochemical properties of as-synthesized composite were studied using cyclic voltammetry (CV), galvanostatic charge discharge (GCD) and electrochemical impedance spectroscopic (EIS) techniques. The novel Cu-TiO2/PPY composite showed enhanced volumetric capacitance ˜714 F cm-1 and gravimetric capacitance ˜674 F g-1 at 1 A g-1. In addition an excellent coulombic efficiency and comparabley low charge transfer resistance than pure PPY suggests improved supercapacitive performance of Cu-TiO2/PPY composite as an electrode material.

Zircon U-Pb and Hf-O isotopes trace the architecture of polymetallic deposits: A case study of the Jurassic ore-forming porphyries in the Qin-Hang metallogenic belt, China

NASA Astrophysics Data System (ADS)

Zhao, Panlao; Yuan, Shunda; Mao, Jingwen; Santosh, M.; Zhang, Dongliang

2017-11-01

The Qin-Hang intra-continental porphyry-skarn Cu polymetallic belt (QHMB) is among the economically important metallogenic belts in South China. The significant differences in the size and metal assemblage of the Jurassic magmatic-hydrothermal ore deposits in this belt remain as an enigma. Here we employ zircon U-Pb and Hf-O isotopes of the Tongshanling and Baoshan Cu-Pb-Zn deposits in the central part of the QHMB to investigate the contrasting metallogenic architecture. Our SIMS zircon U-Pb data indicate that the Tongshanling and Baoshan granodiorite formed at 160 Ma. These rocks show high Mg# values, and negative zircon εHf(t) and high δ18O values suggesting that the magmas of the granodiorite porphyries were mainly generated through the anatexis of older crustal components triggered by the input of mantle-derived magma. The minor content of amphibole phenocrysts, low Sr/Y ratios, negative Eu anomaly, and low zircon Ce4 +/Ce3 + ratios indicate that the porphyries are relatively less oxidized with less water content compared with the ore-bearing porphyries in the Dexing and Yuanzhuding porphyry Cu deposits in the northern and southern part of the QHMB, suggesting that high magmatic water content and oxidation state are important prerequisites for the formation of large size porphyry-skarn copper deposits in the QHMB. The positive correlation between zircon εHf(t) values with the Cu reserves, as well as zircon δ18O values with the Cu/(Cu + Pb + Zn) ratios of the deposits indicate that the magmatic sources exerted a first-order control on the volume and metal assemblage of deposits in the QHMB. The Hf and Nd isotope contour maps indicate that the central part of the QHMB has high potential for Pb-Zn-dominated magmatic-hydrothermal deposits, whereas the northern and southern part of the QHMB are prospective for large Cu deposits. Our results have important implications in formulating regional exploration strategies for Jurassic porphyry-skarn Cu-Pb-Zn deposits in the Qin-Hang belt.

The role of mantle-hybridization and crustal contamination in the petrogenesis of lithospheric mantle-derived alkaline rocks: constraints from Os and Hf isotopes

NASA Astrophysics Data System (ADS)

Mayer, B.; Jung, S.; Brauns, M.; Münker, C.

2018-06-01

The Rhön area as part of the Central European Volcanic Province (CEVP) hosts an unusual suite of Tertiary 24-Ma old hornblende-bearing alkaline basalts that provide insights into melting and fractionation processes within the lithospheric mantle. These chemically primitive to slightly evolved and isotopically (Sr, Nd, Pb) depleted basalts have slightly lower Hf isotopic compositions than respective other CEVP basalts and Os isotope compositions more radiogenic than commonly observed for continental intraplate alkaline basalts. These highly radiogenic initial 187Os/188Os ratios (0.268-0.892) together with their respective Sr-Nd-Pb isotopic compositions are unlikely to result from crustal contamination alone, although a lack of Os data for lower crustal rocks from the area and limited data for CEVP basalts or mantle xenoliths preclude a detailed evaluation. Similarly, melting of the same metasomatized subcontinental lithospheric mantle as inferred for other CEVP basalts alone is also unlikely, based on only moderately radiogenic Os isotope compositions obtained for upper mantle xenoliths from elsewhere in the province. Another explanation for the combined Nd, Sr and Os isotope data is that the lavas gained their highly radiogenic Os isotope composition through a mantle "hybridization", metasomatism process. This model involves a mafic lithospheric component, such as an intrusion of a sublithospheric primary alkaline melt or a melt derived from subducted oceanic material, sometime in the past into the lithospheric mantle where it metasomatized the ambient mantle. Later at 24 Ma, thermal perturbations during rifting forced the isotopically evolved parts of the mantle together with the peridotitic ambient mantle to melt. This yielded a package of melts with highly correlated Re/Os ratios and radiogenic Os isotope compositions. Subsequent movement through the crust may have further altered the Os isotope composition although this effect is probably minor for the majority of the samples based on radiogenic Nd and unradiogenic Sr isotope composition of the lavas. If the radiogenic Os isotope composition can be explained by a mantle-hybridization and metasomatism model, the isotopic compositions of the hornblende basalts can be satisfied by ca. 5-25% addition of the mafic lithospheric component to an asthenospheric alkaline magma. Although a lack of isotope data for all required endmembers make this model somewhat speculative, the results show that the Re-Os isotope system in continental basalts is able to distinguish between crustal contamination and derivation of continental alkaline lavas from isotopically evolved peridotitic lithosphere that was contaminated by mafic material in the past and later remelted during rifting. The Hf isotopic compositions are slightly less radiogenic than in other alkaline basalts from the province and indicate the derivation of the lavas from low Lu-Hf parts of the lithospheric mantle. The new Os and Hf isotope data constrain a new light of the nature of such metasomatizing agents, at least for these particular rocks, which represent within the particular volcanic complex the first product of the volcanism.

The silicon isotope composition of the upper continental crust

NASA Astrophysics Data System (ADS)

Savage, Paul S.; Georg, R. Bastian; Williams, Helen M.; Halliday, Alex N.

2013-05-01

The upper continental crust (UCC) is the major source of silicon (Si) to the oceans and yet its isotopic composition is not well constrained. In an effort to investigate the degree of heterogeneity and provide a robust estimate for the average Si isotopic composition of the UCC, a representative selection of well-characterised, continentally-derived clastic sediments have been analysed using high-precision MC-ICPMS. Analyses of loess samples define a narrow range of Si isotopic compositions (δ30Si = -0.28‰ to -0.15‰). This is thought to reflect the primary igneous mineralogy and predominance of mechanical weathering in the formation of such samples. The average loess δ30Si is -0.22 ± 0.07‰ (2 s.d.), identical to average granite and felsic igneous compositions. Therefore, minor chemical weathering does not resolvably affect bulk rock δ30Si, and loess is a good proxy for the Si isotopic composition of unweathered, crystalline, continental crust. The Si isotopic compositions of shales display much more variability (δ30Si = -0.82‰ to 0.00‰). Shale Si isotope compositions do not correlate well with canonical proxies for chemical weathering, such as CIA values, but do correlate negatively with insoluble element concentrations and Al/Si ratios. This implies that more intensive or prolonged chemical weathering of a sedimentary source, with attendant desilicification, is required before resolvable negative Si isotopic fractionation occurs. Shale δ30Si values that are more positive than those of felsic igneous rocks most likely indicate the presence of marine-derived silica in such samples. Using the data gathered in this study, combined with already published granite Si isotope analyses, a weighted average composition of δ30Si = -0.25 ± 0.16‰ (2 s.d.) for the UCC has been calculated.

Controls on the barium isotope compositions of marine sediments

NASA Astrophysics Data System (ADS)

Bridgestock, Luke; Hsieh, Yu-Te; Porcelli, Donald; Homoky, William B.; Bryan, Allison; Henderson, Gideon M.

2018-01-01

The accumulation of barium (Ba) in marine sediments is considered to be a robust proxy for export production, although this application can be limited by uncertainty in BaSO4 preservation and sediment mass accumulation rates. The Ba isotope compositions of marine sediments could potentially record insights into past changes in the marine Ba cycle, which should be insensitive to these limitations, enabling more robust interpretation of sedimentary Ba as a proxy. To investigate the controls on the Ba isotope compositions of marine sediments and their potential for paleo-oceanographic applications, we present the first Ba isotope compositions results for sediments, as well as overlying seawater depth profiles collected in the South Atlantic. Variations in Ba isotope compositions of the sediments predominantly reflect changes in the relative contributions of detrital and authigenic Ba sources, with open-ocean sediments constraining the isotope composition of authigenic Ba to be δ 138/134Ba ≈ + 0.1 ‰. This value is consistent with the average isotope composition inferred for sinking particulate Ba using simple mass balance models of Ba in the overlying water column and is hypothesized to reflect the removal of Ba from the upper water column with an associated isotopic fractionation of Δ diss-part 138/134Ba ≈ + 0.4 to +0.5. Perturbations to upper ocean Ba cycling, due to changes in export production and the supply of Ba via upwelling, should therefore be recorded by the isotope compositions of sedimentary authigenic Ba. Such insights will help to improve the reliable application of Ba accumulation rates in marine sediments as a proxy for past changes in export production.

Isotopic signals of denitrification in a northern hardwood forested catchment

NASA Astrophysics Data System (ADS)

Wexler, Sarah; Goodale, Christine

2013-04-01

Water samples from streams, groundwater and precipitation were collected during summer from the hydrologic reference watershed (W3) at Hubbard Brook Experimental Forest in the White Mountains, New Hampshire, and analysed for d15N-NO3 and d18O-NO3. Despite very low nitrate concentrations (<0.5 to 8.8 uM NO3-) dual-isotopic signals of sources and processes were clearly distinguishable. The isotopic composition of nitrate from shallow groundwater showed evidence of dual isotopic fractionation in line with denitrification, with a positive relationship between nitrogen and oxygen isotopic composition, a regression line slope of 0.76 (r2 = 0.68), and an empirical isotope enrichment factor of ɛP-S 15N-NO3 -12.7%. The isotopic composition of riparian groundwater nitrate from time-series samples showed variation in processes over a small spatial scale. The expected isotopic composition of nitrate sources in the watershed was used to distinguish nitrate in rain and nitrate from nitrification of both rainfall ammonium and ammonium from mineralised soil organic nitrogen. Evidence of oxygen exchange with water during nitrification was seen in the isotopic composition of stream and shallow groundwater nitrate. The isotopic composition of streamwater nitrate following a period of storms indicated that 25% of nitrate in the streamwater was of atmospheric origin. This suggests rapid infiltration of rainfall via vertical bypass flow to the saturated zone, enabling transport of atmospheric nitrate to the stream channels. Across the Hubbard Brook basin, the isotopic composition of nitrate from paired samples from watersheds 4-7 indicated a switch between a nitrification and assimilation dominated system, to a system influenced by rainfall nitrogen inputs and denitrification. The dual isotope approach has revealed evidence of denitrification of nitrate from different sources at low concentrations at Hubbard Brook during summer. This isotopic evidence deepens our understanding of the significance and spatial variability of denitrification in environments with low levels of nitrate, represented by this northern hardwood forested catchment.

Cooperative cytotoxic activity of Zn and Cu in bovine serum albumin-conjugated ZnS/CuS nano-composites in PC12 cancer cells

NASA Astrophysics Data System (ADS)

Wang, Hua-Jie; Yu, Xue-Hong; Wang, Cai-Feng; Cao, Ying

2013-11-01

Series of self-assembled and mono-dispersed bovine serum albumin (BSA)-conjugated ZnS/CuS nano-composites with different Zn/Cu ratios had been successfully synthesized by a combination method of the biomimetic synthesis and ion-exchange strategy under the gentle conditions. High-resolution transmission electron microscopy observation, Fourier transform infrared spectra and zeta potential analysis demonstrated that BSA-conjugated ZnS/CuS nano-composites with well dispersity had the hierarchical structure and BSA was a key factor to control the morphology and surface electro-negativity of final products. The real-time monitoring by atomic absorption spectroscopy and powder X-ray diffraction revealed that the Zn/Cu ratio of nano-composites could be controlled by adjusting the ion-exchange time. In addition, the metabolic and morphological assays indicated that the metabolic proliferation and spread of rat pheochromocytoma (PC12) cells could be inhibited by nano-composites, with the high anti-cancer activity at a low concentration (4 ppm). What were more important, Zn and Cu in nano-composites exhibited a positive cooperativity at inhibiting cancer cell functions. The microscope observation and biochemical marker analysis clearly revealed that the nano-composites-included lipid peroxidation and disintegration of membrane led to the death of PC12 cells. Summarily, the present study substantiated the potential of BSA-conjugated ZnS/CuS nano-composites as anti-cancer drug.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Valysaev, B.M.; Erokhin, V.E.; Grinchenko, Y.I.

A study has been made of the isotopic composition of the carbon in methane and carbon dioxide, as well as hydrogen in the methane, in the gases of mud volcanoes, for all main mud volcano areas in the USSR. The isotopic composition of carbon and hydrogen in methane shows that the gases resemble those of oil and gas deposits, while carbon dioxide of these volcanoes has a heavier isotopic composition with a greater presence of ''ultraheavy'' carbon dioxide. By the chemical and isotopic composition of gases, Azerbaidzhan and South Sakhalin types of mud volcano gases have been identified, as wellmore » as Bulganak subtypes and Akhtala and Kobystan varieties. Correlations are seen between the isotopic composition of gases and the geological build of mud volcano areas.« less

Stable isotopic composition of perchlorate and nitrate accumulated in plants: Hydroponic experiments and field data.

PubMed

Estrada, Nubia Luz; Böhlke, J K; Sturchio, Neil C; Gu, Baohua; Harvey, Greg; Burkey, Kent O; Grantz, David A; McGrath, Margaret T; Anderson, Todd A; Rao, Balaji; Sevanthi, Ritesh; Hatzinger, Paul B; Jackson, W Andrew

2017-10-01

Natural perchlorate (ClO 4 - ) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ 37 Cl, δ 18 O, and Δ 17 O), indicating that ClO 4 - may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO 4 - , but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO 4 - in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO 4 - was transported from solutions into plants similarly to NO 3 - but preferentially to Cl - (4-fold). The ClO 4 - isotopic compositions of initial ClO 4 - reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO 4 - uptake or accumulation. The ClO 4 - isotopic composition of field-grown snap beans was also consistent with that of ClO 4 - in varying proportions from irrigation water and precipitation. NO 3 - uptake had little or no effect on NO 3 - isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε ( 15 N/ 18 O) ratio of 1.05 was observed between NO 3 - in hydroponic solutions and leaf extracts, consistent with partial NO 3 - reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO 4 - in commercial produce, as illustrated by spinach, for which the ClO 4 - isotopic composition was similar to that of indigenous natural ClO 4 - . Our results indicate that some types of plants can accumulate and (presumably) release ClO 4 - to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO 4 - and NO 3 - in plants may be useful for determining sources of fertilizers and sources of ClO 4 - in their growth environments and consequently in food supplies. Copyright © 2017 Elsevier B.V. All rights reserved.

Stable isotopic composition of perchlorate and nitrate accumulated in plants: Hydroponic experiments and field data

USGS Publications Warehouse

Estrada, Nubia Luz; Böhlke, John Karl; Sturchio, Neil C.; Gu, Baohua; Harvey, Greg; Burkey, Kent O.; Grantz, David A.; McGrath, Margaret T.; Anderson, Todd A.; Rao, Balaji; Sevanthi, Ritesh; Hatzinger, Paul B.; Jackson, W. Andrew

2017-01-01

Natural perchlorate (ClO4−) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ37Cl, δ18O, and Δ17O), indicating that ClO4− may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO4−, but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO4− in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO4− was transported from solutions into plants similarly to NO3− but preferentially to Cl− (4-fold). The ClO4− isotopic compositions of initial ClO4− reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO4− uptake or accumulation. The ClO4− isotopic composition of field-grown snap beans was also consistent with that of ClO4− in varying proportions from irrigation water and precipitation. NO3− uptake had little or no effect on NO3− isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε (15N/18O) ratio of 1.05 was observed between NO3− in hydroponic solutions and leaf extracts, consistent with partial NO3− reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO4− in commercial produce, as illustrated by spinach, for which the ClO4− isotopic composition was similar to that of indigenous natural ClO4−. Our results indicate that some types of plants can accumulate and (presumably) release ClO4− to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO4−and NO3− in plants may be useful for determining sources of fertilizers and sources of ClO4− in their growth environments and consequently in food supplies.

Tracing Cd, Zn and Pb pollution sources in bivalves using isotopes

NASA Astrophysics Data System (ADS)

Shiel, A. E.; Weis, D. A.; Orians, K. J.

2010-12-01

In a multi-tracer study, Cd, Zn and Pb isotopes (MC-ICP-MS) and elemental concentrations (HR-ICP-MS) are evaluated as tools to distinguish between natural and anthropogenic sources of these metals in bivalves from western Canada (British Columbia), the eastern USA, Hawaii and France. High Cd concentrations found in BC oysters have elicited economic and health concerns. The source of these high Cd levels is unknown but thought to be largely natural. High Cd levels in BC oysters are largely attributed to the natural upwelling of Cd-rich intermediate waters in the North Pacific as the δ114/110Cd (-0.69 to -0.09‰) and δ66/64Zn (0.28 to 0.36‰) values of BC oysters fall within the range reported for North Pacific seawater. Different contributions from anthropogenic sources account for the variability of Cd isotopic compositions of BC oysters; the lightest of these oysters are from the BC mainland. These oysters also have Pb isotopic compositions that reflect primarily anthropogenic sources (e.g., leaded and unleaded automotive gasoline and smelting of Pb ores, potentially historical). On the contrary, USA East Coast bivalves exhibit relatively light Cd isotopic compositions (δ114/110Cd = -1.20 to -0.54‰; lighter than reported for North Atlantic seawater) due to the high prevalence of industry on this coast. The Pb isotopic compositions of these bivalves indicate contributions from the combustion of coal. The large variability of environmental health among coastal areas in France is reflected in the broad range of Cd isotopic compositions exhibited by French bivalves (δ114/110Cd = -1.08 to -0.20‰). Oysters and mussels from the Marennes-Oléron basin and Gironde estuary have the lightest Cd isotopic compositions of the French oysters consistent with significant historical Cd emissions from the now-closed proximal Zn smelter. In these bivalves, significant declines in the Cd levels between 1984/7 and 2004/5 are not accompanied by a significant shift in the Cd isotopic composition toward natural values. The Mediterranean samples have isotopic compositions within error of the lighter end of the range reported for Mediterranean seawater. The Zn isotopic compositions of French oysters and mussels (δ66/64Zn = 0.39 to 0.46‰) are identical to those reported for North Atlantic seawater, with the exception of the much heavier compositions of oysters (δ66/64Zn = 1.03 to 1.15‰) from the polluted Gironde estuary. In agreement with Cd and Zn isotopic compositions, the Pb isotopic compositions of the French bivalves indicate primarily industrial (as opposed to automotive) sources; this is consistent with the collection of most of the French bivalve samples in 2004, after the complete phase-out of leaded gasoline in France. This study demonstrates the effective use of Cd and Zn isotopes to trace anthropogenic sources in the environment and the benefit of combining these tools with Pb isotope “fingerprinting” techniques to identify processes contributing metals. Use of these new geochemical tools requires site-specific knowledge of potential metal sources and their isotopic compositions.

Kinetics and mechanics of photo-polymerized triazole-containing thermosetting composites via the copper(I)-catalyzed azide-alkyne cycloaddition

PubMed Central

Song, Han Byul; Wang, Xiance; Patton, James R.; Stansbury, Jeffrey W.; Bowman, Christopher N.

2017-01-01

Objectives Several features necessary for polymer composite materials in practical applications such as dental restorative materials were investigated in photo-curable CuAAC (copper(I)-catalyzed azide-alkyne cycloaddition) thermosetting resin-based composites with varying filler loadings and compared to a conventional BisGMA/TEGDMA based composite. Methods Tri-functional alkyne and di-functional azide monomers were synthesized for CuAAC resins and incorporated with alkyne-functionalized silica microfillers for CuAAC composites. Polymerization kinetics, in situ temperature change, and shrinkage stress were monitored simultaneously with a tensometer coupled with FTIR spectroscopy and a data-logging thermocouple. The glass transition temperature was analyzed by dynamic mechanical analysis. Flexural modulus/strength and flexural toughness were characterized in three-point bending on a universal testing machine. Results The photo-CuAAC polymerization of composites containing between 0 and 60 wt% microfiller achieved ~99% conversion with a dramatic reduction in the maximum heat of reaction (~20 °C decrease) for the 60 wt% filled CuAAC composites as compared with the unfilled CuAAC resin. CuAAC composites with 60 wt% microfiller generated more than twice lower shrinkage stress of 0.43±0.01 MPa, equivalent flexural modulus of 6.1±0.7 GPa, equivalent flexural strength of 107±9 MPa, and more than 10 times higher energy absorption of 10±1 MJ m−3 when strained to 11% relative to BisGMA-based composites at equivalent filler loadings. Significance Mechanically robust and highly tough, photo-polymerized CuAAC composites with reduced shrinkage stress and a modest reaction exotherm were generated and resulted in essentially complete conversion. PMID:28363645

Kinetics and mechanics of photo-polymerized triazole-containing thermosetting composites via the copper(I)-catalyzed azide-alkyne cycloaddition.

PubMed

Song, Han Byul; Wang, Xiance; Patton, James R; Stansbury, Jeffrey W; Bowman, Christopher N

2017-06-01

Several features necessary for polymer composite materials in practical applications such as dental restorative materials were investigated in photo-curable CuAAC (copper(I)-catalyzed azide-alkyne cycloaddition) thermosetting resin-based composites with varying filler loadings and compared to a conventional BisGMA/TEGDMA based composite. Tri-functional alkyne and di-functional azide monomers were synthesized for CuAAC resins and incorporated with alkyne-functionalized glass microfillers for CuAAC composites. Polymerization kinetics, in situ temperature change, and shrinkage stress were monitored simultaneously with a tensometer coupled with FTIR spectroscopy and a data-logging thermocouple. The glass transition temperature was analyzed by dynamic mechanical analysis. Flexural modulus/strength and flexural toughness were characterized in three-point bending on a universal testing machine. The photo-CuAAC polymerization of composites containing between 0 and 60wt% microfiller achieved ∼99% conversion with a dramatic reduction in the maximum heat of reaction (∼20°C decrease) for the 60wt% filled CuAAC composites as compared with the unfilled CuAAC resin. CuAAC composites with 60wt% microfiller generated more than twice lower shrinkage stress of 0.43±0.01MPa, equivalent flexural modulus of 6.1±0.7GPa, equivalent flexural strength of 107±9MPa, and more than 10 times higher energy absorption of 10±1MJm -3 when strained to 11% relative to BisGMA-based composites at equivalent filler loadings. Mechanically robust and highly tough, photo-polymerized CuAAC composites with reduced shrinkage stress and a modest reaction exotherm were generated and resulted in essentially complete conversion. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

VEGF-Iron Oxide Conjugate for Dual MR and PET Imaging of Breast Cancer Angiogenesis

DTIC Science & Technology

2007-09-01

with both VEGF121 and PET isotope 64Cu (t1/2 = 12.7 h) and test the dual probe in vitro. Aim 2: To test the PET and mMRI efficacy of the dual...iron oxide nanoparticles conjugated with macrocyclic chelating agent DOTA for 64Cu -labeling and cyclic RGD peptide for integrin alpha(v)beta(3...radionuclide 64Cu without loss of receptor affinity and functional activity of the protein. 64Cu -VEGF is also able to delineate small tumors that are

Stable water isotope patterns in a climate change hotspot: the isotope hydrology framework of Corsica (western Mediterranean).

PubMed

van Geldern, Robert; Kuhlemann, Joachim; Schiebel, Ralf; Taubald, Heinrich; Barth, Johannes A C

2014-06-01

The Mediterranean is regarded as a region of intense climate change. To better understand future climate change, this area has been the target of several palaeoclimate studies which also studied stable isotope proxies that are directly linked to the stable isotope composition of water, such as tree rings, tooth enamel or speleothems. For such work, it is also essential to establish an isotope hydrology framework of the region of interest. Surface waters from streams and lakes as well as groundwater from springs on the island of Corsica were sampled between 2003 and 2009 for their oxygen and hydrogen isotope compositions. Isotope values from lake waters were enriched in heavier isotopes and define a local evaporation line (LEL). On the other hand, stream and spring waters reflect the isotope composition of local precipitation in the catchment. The intersection of the LEL and the linear fit of the spring and stream waters reflect the mean isotope composition of the annual precipitation (δP) with values of-8.6(± 0.2) ‰ for δ(18)O and-58(± 2) ‰ for δ(2)H. This value is also a good indicator of the average isotope composition of the local groundwater in the island. Surface water samples reflect the altitude isotope effect with a value of-0.17(± 0.02) ‰ per 100 m elevation for oxygen isotopes. At Vizzavona Pass in central Corsica, water samples from two catchments within a lateral distance of only a few hundred metres showed unexpected but systematic differences in their stable isotope composition. At this specific location, the direction of exposure seems to be an important factor. The differences were likely caused by isotopic enrichment during recharge in warm weather conditions in south-exposed valley flanks compared to the opposite, north-exposed valley flanks.

Hadean Oceanography: Experimental Constraints on the Development of the Terrestrial Hydrosphere and the Origin of Life on Earth

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryerson, F J

The oxygen isotopic compositions of the world's oldest mineral grains, zircon, have recently been used to infer the compositions of the rocks from which they crystallized. The results appear to require a source that had once experienced isotopic fractionation between clay minerals and liquid water, thereby implying the presence of liquid water at the Earth's surface prior to 4.4 billion years ago, less than 2 million years after accretion. This observation has important implications for the development of the Earth's continental crust. The inferred composition of the zircon source rock is directly dependent upon the oxygen isotopic fractionation between zirconmore » and melt, and zircon and water. These fractionation factors have not been determined experimentally, however, constituting the weak link in this argument. A series of experiments to measure these fractionation factors has been conducted. The experiments consist of finely powdered quartz, a polished single crystal of zircon and isotopically-enriched or isotopically normal water to provide a range of isotopic compositions. The experiments will be run until quartz is in isotopic equilibrium with water. Zircon was expected to partially equilibrate producing an oxygen isotopic diffusion profile perpendicular to the surface. Ion probe spot analysis of quartz and depth profiling of zircon will determine the bulk and surface isotopic compositions of the phases, respectively. The well-known quartz-water isotopic fractionation factors can be used to calculate the oxygen isotopic composition of the fluid, and with the zircon surface composition, the zircon-water fractionation factor. Run at temperatures up to 1000 C for as long as 500 hours have not produced diffusion profiles longer than 50 nm. The steep isotopic gradient at the samples surface precludes use of the diffusion profile for estimation on the surface isotopic composition. The short profiles may be the result of surface dissolution, although such dissolution cannot be resolved in SEM images. The sluggish nature of diffusion in zircon may require that fractionation factors be determined by direct hydrothermal synthesis of zircon rather than by mineral-fluid exchange.« less

Iron and nickel isotope compositions of presolar silicon carbide grains from supernovae

NASA Astrophysics Data System (ADS)

Kodolányi, János; Stephan, Thomas; Trappitsch, Reto; Hoppe, Peter; Pignatari, Marco; Davis, Andrew M.; Pellin, Michael J.

2018-01-01

We report the carbon, silicon, iron, and nickel isotope compositions of twenty-five presolar SiC grains of mostly supernova (SN) origin. The iron and nickel isotope compositions were measured with the new Chicago Instrument for Laser Ionization, CHILI, which allows the analysis of all iron and nickel isotopes without the isobaric interferences that plagued previous measurements with the NanoSIMS. Despite terrestrial iron and nickel contamination, significant isotopic anomalies in 54Fe/56Fe, 57Fe/56Fe, 60Ni/58Ni, 61Ni/58Ni, 62Ni/58Ni, and 64Ni/58Ni were detected in nine SN grains (of type X). Combined multi-isotope data of three grains with the largest nickel isotope anomalies (>100‰ or <-100‰ in at least one isotope ratio, when expressed as deviation from the solar value) are compared with the predictions of two SN models, one with and one without hydrogen ingestion in the He shell prior to SN explosion. One grain's carbon-silicon-iron-nickel isotope composition is consistent with the prediction of the model without hydrogen ingestion, whereas the other two grains' isotope anomalies could not be reproduced using either SN models. The discrepancies between the measured isotope compositions and model predictions may indicate element fractionation in the SN ejecta prior to or during grain condensation, and reiterate the need for three-dimensional SN models.

Paleoceanographic conditions on the São Paulo Ridge, SW Atlantic Ocean, for the past 30 million years inferred from Os and Pb isotopes of a hydrogenous ferromanganese crust

NASA Astrophysics Data System (ADS)

Goto, Kosuke T.; Nozaki, Tatsuo; Toyofuku, Takashi; Augustin, Adolpho H.; Shimoda, Gen; Chang, Qing; Kimura, Jun-Ichi; Kameo, Koji; Kitazato, Hiroshi; Suzuki, Katsuhiko

2017-12-01

Hydrogenous ferromanganese (Fe-Mn) crusts can provide records of long-term environmental changes during the Cenozoic. To understand the paleoceanographic conditions in the southwestern Atlantic Ocean, we investigated depth profiles of major- and trace-element concentrations as well as Os and Pb isotopic compositions in a Fe-Mn crust collected from the southern flank of the São Paulo Ridge in the southwestern Atlantic. Major and trace element data plotted on ternary Mn-Fe-10×(Ni+Co+Cu) and rare-earth element plus yttrium (REY) discrimination diagrams indicate that the analyzed sample is a typical hydrogenous Fe-Mn crust. The obtained 187Os/188Os data were matched to the Cenozoic seawater Os isotope evolution curve reconstructed from pelagic sediments. The result suggests that the Fe-Mn crust has accreted over 30 Myr with growth rates of 0.5-3 mm/Myr, although the sample likely grew in two directions during the early stage of its growth. We found no evidence of growth hiatus in the sample, which may contrast with the growth histories of many Pacific Fe-Mn crusts. Hence, the conditions favorable for the accretion of hydrogenous Fe-Mn crusts were likely to have developed on the São Paulo Ridge over the past 30 Myr. The Pb isotopic compositions show very limited ranges (e.g., 206Pb/204Pb=18.80-18.85), and are similar to those of pre-anthropogenic seawater in the Southern Ocean. As the São Paulo Ridge is located near the Vema Channel, which is presently a major path of Antarctic Bottom Water, we suggest that a strong northward bottom current has continuously swept detrital and biogenic sediments from the ridge, and played a vital role in the Fe-Mn crust formation since 30 Ma.

Examination of chloritization of biotite as a tool for reconstructing the physicochemical parameters of mineralization and associated alteration in the Zafarghand porphyry copper system, Ardestan, Central Iran: mineral-chemistry and stable isotope analyses

NASA Astrophysics Data System (ADS)

Aminroayaei Yamini, Maryam; Tutti, Faramarz; Aminoroayaei Yamini, Mohammad Reza; Ahmadian, Jamshid; Wan, Bo

2017-10-01

The chloritization of biotite and stable isotopes of silicate have been studied for the Zafarghand porphyry copper deposit, Ardestan, Iran. The studied area, in the central part of the Urumieh-Dokhtar magmatic belt, contains porphyry-style Cu mineralization and associated hydrothermal alteration within the Miocene (19-26 Ma, Zircon U-Pb age) granodioritc stock and adjacent andesitic to rhyodacitic volcanic rocks (ca. 56 Ma, zircon U-Pb age). The primary and secondary biotite that formed during potassic alteration in this porphyry and these volcanic host rocks are variably chloritized. Chloritization of biotite pseudomorphically is characterized by an increase in MgO, FeOt, and MnO, with decreasing in SiO2, K2O, and TiO2. Based on the Ti-in-biotite geothermometer of Henry et al. (Am Mineral 90:316-328, 2005) and Al-in-chlorite geothermometer of Cathelineau (Clay Miner 23:417-485, 1988), crystallization temperatures of primary biotite representative of magmatic conditions and later chloritization temperature range from 617° to 675 °C ± 24 °C and 177° to 346 °C, respectively. Calculated isotopic compositions of fluids that chloritized primary and secondary biotite display isotopic compositions of 1.1 to 1.7 per mil for δ18O and -19.9 to -20.5 per mil for δD consistent with meteoric water. Sericite, barren, and A-type-quartz veins from phyllic alteration were produced by mixed magmatic and meteoric water with δ18O values from -2.8 to 2.5 and δD values of ˜ -23 per mil; the narrow range of δD values of the propylitic epidote may be due to a meteoric water with δ18O values from 0.8 to 1.6 and δD values from -14.6 to -16.9 per mil.

Effect of Cu2O morphology on photocatalytic hydrogen generation and chemical stability of TiO2/Cu2O composite.

PubMed

Zhu, Lihong; Zhang, Junying; Chen, Ziyu; Liu, Kejia; Gao, Hong

2013-07-01

Improving photocatalytic activity and stability of TiO2/Cu2O composite is a challenge in generating hydrogen from water. In this paper, the TiO2 film/Cu2O microgrid composite was prepared via a microsphere lithography technique, which possesses a remarkable performance of producing H2 under UV-vis light irradiation, in comparison with pure TiO2 film, Cu2O film and TiO2 film/Cu2O film. More interesting is that in TiO2 film/Cu2O microgrid, photo-corrosion of Cu2O can be retarded. After deposition of Pt on its surface, the photocatalytic activity of TiO2/Cu2O microgrid in producing H2 is improved greatly.

Yttrium enrichment and improved magnetic properties in partially melted Y-Ba-Cu-O materials

NASA Technical Reports Server (NTRS)

Alterescu, Sidney; Hojaji, Hamid; Barkatt, Aaron; Michael, Karen A.; Hu, Shouxiang

1990-01-01

The yttrium-rich compositions in the Y-Ba-Cu-O system were mapped out in a systematic manner to quantify their magnetic properties and to correlate them with the microstructure and phase composition as determined by scanning electron microscopy and X-ray diffraction analysis. It is found that the microstructure of Y-Ba-Cu-O compositions is a sensitive function of both their composition and processing conditions. Measurements of magnetic susceptibility and maximum (low-field) and remanent magnetization for the system Y:Ba:Cu = x:2:3 show highest values for x = 2. The corresponding structures involve numerous small crystals of Y2BaCuO5 (211) embedded in highly ordered assemblages of continous YBa2Cu3O(7-y) (123) layers.

Reconstruction of the Nd isotope composition of seawater on epicontinental seas: Testing the potential of Fe-Mn oxyhydroxide coatings on foraminifera tests for deep-time investigations

NASA Astrophysics Data System (ADS)

Charbonnier, Guillaume; Pucéat, Emmanuelle; Bayon, Germain; Desmares, Delphine; Dera, Guillaume; Durlet, Christophe; Deconinck, Jean-François; Amédro, Francis; Gourlan, Alexandra T.; Pellenard, Pierre; Bomou, Brahimsamba

2012-12-01

The Fe-Mn oxide fraction leached from deep-sea sediments has been increasingly used to reconstruct the Nd isotope composition of deep water masses, that can be used to track changes in oceanic circulation with a high temporal resolution. Application of this archive to reconstruct the Nd isotope composition of bottom seawater in shallow shelf environments remained however to be tested. Yet as the Nd isotope composition of seawater on continental margins is particularly sensitive to changes in erosional inputs, establishment of neritic seawater Nd isotope evolution around areas of deep water formation would be useful to discriminate the influence of changes in oceanic circulation and in isotopic composition of erosional inputs on the Nd isotope record of deep waters. The purpose of this study is to test the potential of Fe-Mn coatings leached from foraminifera tests to reconstruct the Nd isotope composition of seawater in shelf environments for deep-time intervals. Albian to Turonian samples from two different outcrops have been recovered, from the Paris Basin (Wissant section, northern France) and from the Western Interior Seaway (Hot Spring, South Dakota, USA), that were deposited in epicontinental seas. Rare Earth Element (REE) spectra enriched in middle REEs in the foraminifera leach at Wissant highlight the presence of Fe-Mn oxides. The similarity of the Nd isotopic signal of the Fe-Mn oxide fraction leached from foraminifera tests with that of fish teeth suggests that Fe-Mn oxides coating foraminifera can be good archives of shelf bottom seawater Nd isotopic composition. Inferred bottom shelf water Nd isotope compositions at Wissant range from -8.5 to -9.7 ɛ-units, about 1.5-2 ɛ-units higher than that of the contemporaneous local detrital fraction. At Hot Spring, linear REE spectra characterizing foraminifera leach may point to an absence of authigenic marine Fe-Mn oxide formation in this area during the Late Cenomanian-Early Turonian, consistent with dysoxic to anoxic conditions at Hot Spring, contemporaneous to an Oceanic Anoxic Event. The similarity of the Nd isotopic signal of the carbonate matrix of foraminifera with that of fish teeth suggests that it records the Nd isotope composition of bottom shelf seawater as well. Inferred bottom shelf water Nd isotope compositions at Hot Spring are quite radiogenic, between -7 and -6 ɛ-units, about 2.5-4 ɛ-units higher than that of the contemporaneous local detrital fraction. In contrast, in both sections Fe-Mn oxides leached directly from the decarbonated sediment tend to yield a less radiogenic Nd isotopic composition, typically between 0.2 and 0.8 ɛ-units lower, that is intermediate between that of fish teeth and of the detrital fraction. This suggests the contribution of pre-formed continental Fe-Mn oxides to the Nd isotopic signal, along with authigenic marine oxides, or a detrital contamination during leaching.

Hydrogen and oxygen in brine shrimp chitin reflect environmental water and dietary isotopic composition

NASA Astrophysics Data System (ADS)

Nielson, Kristine E.; Bowen, Gabriel J.

2010-03-01

Hydrogen and oxygen isotope ratios of the common structural biopolymer chitin are a potential recorder of ecological and environmental information, but our understanding of the mechanisms of incorporation of H and O from environmental substrates into chitin is limited. We report the results of a set of experiments in which the isotopic compositions of environmental water and diet were varied independently in order to assess the contribution of these variables to the H and O isotopic composition of Artemia franciscana chitin. Hydrogen isotope ratios of chitin were strongly linearly correlated with both food and water, with approximately 26% of the hydrogen signal reflecting food and approximately 38% reflecting water. Oxygen isotopes were also strongly correlated with the isotopic composition of water and food, but whereas 69% of oxygen in chitin exchanged with environmental water, only 10% was derived from food. We propose that these observations reflect the position-specific, partial exchange of H and O atoms with brine shrimp body water during the processes of digestion and chitin biosynthesis. Comparison of culture experiments with a set of natural samples collected from the Great Salt Lake, UT in 2006 shows that, with some exceptions, oxygen isotope compositions of chitin track those of water, whereas hydrogen isotopes vary inversely with those of lake water. The different behavior of the two isotopic systems can be explained in terms of a dietary shift from allochthonous particulate matter with relatively higher δ 2H values in the early spring to autochthonous particulate matter with significantly lower δ 2H values in the late summer to autumn. These results suggest oxygen in chitin may be a valuable proxy for the oxygen isotopic composition of environmental water, whereas hydrogen isotope values from the same molecule may reveal ecological and biogeochemical changes within lakes.

Isotopologue Distributions of Peptide Product Ions by Tandem Mass Spectrometry: Quantitation of Low Levels of Deuterium Incorporation1

PubMed Central

Wang, Benlian; Sun, Gang; Anderson, David R.; Jia, Minghong; Previs, Stephen; Anderson, Vernon E.

2007-01-01

Protonated molecular peptide ions and their product ions generated by tandem mass spectrometry appear as isotopologue clusters due to the natural isotopic variations of carbon, hydrogen, nitrogen, oxygen and sulfur. Quantitation of the isotopic composition of peptides can be employed in experiments involving isotope effects, isotope exchange, isotopic labeling by chemical reactions, and studies of metabolism by stable isotope incorporation. Both ion trap and quadrupole-time of flight mass spectrometry are shown to be capable of determining the isotopic composition of peptide product ions obtained by tandem mass spectrometry with both precision and accuracy. Tandem mass spectra obtained in profile-mode of clusters of isotopologue ions are fit by non-linear least squares to a series of Gaussian peaks (described in the accompanying manuscript) which quantify the Mn/M0 values which define the isotopologue distribution (ID). To determine the isotopic composition of product ions from their ID, a new algorithm that predicts the Mn/M0 ratios is developed which obviates the need to determine the intensity of all of the ions of an ID. Consequently a precise and accurate determination of the isotopic composition a product ion may be obtained from only the initial values of the ID, however the entire isotopologue cluster must be isolated prior to fragmentation. Following optimization of the molecular ion isolation width, fragmentation energy and detector sensitivity, the presence of isotopic excess (2H, 13C, 15N, 18O) is readily determined within 1%. The ability to determine the isotopic composition of sequential product ions permits the isotopic composition of individual amino acid residues in the precursor ion to be determined. PMID:17559791

Nucleosynthetic Heterogeneity Controls Vanadium Isotope Variations in Bulk Chondrites

NASA Technical Reports Server (NTRS)

Nielsen, S. G.; Righter, K.; Wu, F.; Owens, J. D.; Prytulak, J.; Burton, K.; Parkinson, I.; Davis, D.

2018-01-01

The vanadium (V) isotope composition of early solar system materials have been hypothesized to be sensitive to high energy irradiation that originated from the young Sun. Vanadium has two isotopes with masses 50 and 51 that have (51)V/(50)V ratio of approximately 410. High energy irradiation produces (50)V from various target isotopes of Ti, Cr and Fe, which would result in light V isotope compositions (expressed as delta (51)V in per mille = 1000 x (((51)V/(50)V(sub sample)/(51)V/(50)V(sub AlfaAesar)) - 1)) relative to a presumably chondritic starting composition. Recently published V isotope data for calcium aluminium inclusions (CAIs) has revealed some very negative values relative to chondrites (by almost -4 per mille) that were indeed interpreted to reflect irradiation processes despite the fact that the studied CAIs all exhibited significant initial abundances of (10)Be, while only a few CAIs displayed light V isotope compositions. It is difficult to relate V isotope variations directly to a singular process because V only possesses two isotopes. Therefore, V isotope variations can principally be produced both mass dependent and independent processes. Mass dependent kinetic stable isotope fractionation is common in CAIs for refractory elements due to partial condensation/evaporation processes. The element strontium (Sr) has an almost identical condensation temperature to V and studies of stable Sr isotope compositions in CAIs reveal both heavy and light values relative to chondrites of several permil. These variations are similar in magnitude to those reported for V isotopes in CAIs, which suggests it is possible that some of the V isotope variation in CAIs could be due to kinetic stable isotope fractionation during condensation/evaporation processes.

The stable isotope composition of nitrogen and carbon and elemental contents in modern and fossil seabird guano from Northern Chile - Marine sources and diagenetic effects.

PubMed

Lucassen, Friedrich; Pritzkow, Wolfgang; Rosner, Martin; Sepúlveda, Fernando; Vásquez, Paulina; Wilke, Hans; Kasemann, Simone A

2017-01-01

Seabird excrements (guano) have been preserved in the arid climate of Northern Chile since at least the Pliocene. The deposits of marine organic material in coastal areas potentially open a window into the present and past composition of the coastal ocean and its food web. We use the stable isotope composition of nitrogen and carbon as well as element contents to compare the principal prey of the birds, the Peruvian anchovy, with the composition of modern guano. We also investigate the impact of diagenetic changes on the isotopic composition and elemental contents of the pure ornithogenic sediments, starting with modern stratified deposits and extending to fossil guano. Where possible, 14C systematics is used for age information. The nitrogen and carbon isotopic composition of the marine prey (Peruvian anchovy) of the birds is complex as it shows strong systematic variations with latitude. The detailed study of a modern profile that represents a few years of guano deposition up to present reveals systematic changes in nitrogen and carbon isotopic composition towards heavier values that increase with age, i.e. depth. Only the uppermost, youngest layers of modern guano show compositional affinity to the prey of the birds. In the profile, the simultaneous loss of nitrogen and carbon occurs by degassing, and non-volatile elements like phosphorous and calcium are passively enriched in the residual guano. Fossil guano deposits are very low in nitrogen and low in carbon contents, and show very heavy nitrogen isotopic compositions. One result of the study is that the use of guano for tracing nitrogen and carbon isotopic and elemental composition in the marine food web of the birds is restricted to fresh material. Despite systematic changes during diagenesis, there is little promise to retrieve reliable values of marine nitrogen and carbon signatures from older guano. However, the changes in isotopic composition from primary marine nitrogen isotopic signatures towards very heavy values generate a compositionally unique material. These compositions trace the presence of guano in natural ecosystems and its use as fertilizer in present and past agriculture.

The stable isotope composition of nitrogen and carbon and elemental contents in modern and fossil seabird guano from Northern Chile – Marine sources and diagenetic effects

PubMed Central

Pritzkow, Wolfgang; Rosner, Martin; Sepúlveda, Fernando; Vásquez, Paulina; Wilke, Hans; Kasemann, Simone A.

2017-01-01

Seabird excrements (guano) have been preserved in the arid climate of Northern Chile since at least the Pliocene. The deposits of marine organic material in coastal areas potentially open a window into the present and past composition of the coastal ocean and its food web. We use the stable isotope composition of nitrogen and carbon as well as element contents to compare the principal prey of the birds, the Peruvian anchovy, with the composition of modern guano. We also investigate the impact of diagenetic changes on the isotopic composition and elemental contents of the pure ornithogenic sediments, starting with modern stratified deposits and extending to fossil guano. Where possible, 14C systematics is used for age information. The nitrogen and carbon isotopic composition of the marine prey (Peruvian anchovy) of the birds is complex as it shows strong systematic variations with latitude. The detailed study of a modern profile that represents a few years of guano deposition up to present reveals systematic changes in nitrogen and carbon isotopic composition towards heavier values that increase with age, i.e. depth. Only the uppermost, youngest layers of modern guano show compositional affinity to the prey of the birds. In the profile, the simultaneous loss of nitrogen and carbon occurs by degassing, and non-volatile elements like phosphorous and calcium are passively enriched in the residual guano. Fossil guano deposits are very low in nitrogen and low in carbon contents, and show very heavy nitrogen isotopic compositions. One result of the study is that the use of guano for tracing nitrogen and carbon isotopic and elemental composition in the marine food web of the birds is restricted to fresh material. Despite systematic changes during diagenesis, there is little promise to retrieve reliable values of marine nitrogen and carbon signatures from older guano. However, the changes in isotopic composition from primary marine nitrogen isotopic signatures towards very heavy values generate a compositionally unique material. These compositions trace the presence of guano in natural ecosystems and its use as fertilizer in present and past agriculture. PMID:28594902

Microstructure and Mechanical Properties of C/C Composite/TC17 Joints with Ag-Cu-Ti Brazing Alloy

NASA Astrophysics Data System (ADS)

Cao, Xiujie; Zhu, Ying; Guo, Wei; Peng, Peng; Ma, Kaituo

2017-12-01

Carbon/Carbon composite(C/C) was vacuum brazed to titanium alloy (TC17) using Ag-Cu-Ti brazing alloy. The effects of brazing temperature on the interfacial microstructure and joint properties were investigated by energy dispersive spectrometer (EDS), a scanning electron microscope (SEM), X-ray diffraction (XRD) and Gleeble1500D testing machine. Results show that C/C composite and TC17 were successfully brazed using AgCuTi brazing alloy. Various phases including TiC, Ag(s, s), Cu(s, s), Ti3Cu4, TiCu, and Ti2Cu were formed in the brazed joint. The maximum shear strength of the brazed joints with AgCuTi brazing alloy was 24±1 MPa when brazed at 860°C for 15 min.

Seasonality of Leaf Carbon Isotopic Composition and Leaf Water Isotopic Enrichment in a Mixed Evergreen Forest in Southern California

NASA Astrophysics Data System (ADS)

Santiago, L. S.; Sickman, J. O.; Goulden, M.; DeVan, C.; Pasquini, S. C.; Pivovaroff, A. L.

2011-12-01

Leaf carbon isotopic composition and leaf water isotopic enrichment reflect physiological processes and are important for linking local and regional scale processes to global patterns. We investigated how seasonality affects the isotopic composition of bulk leaf carbon, leaf sugar carbon, and leaf water hydrogen under a Mediterranean climate. Leaf and stem samples were collected monthly from four tree species (Calocedrus decurrens, Pinus lambertiana, Pinus ponderosa, and Quercus chrysolepis) at the James San Jacinto Mountain Reserve in southern California. Mean monthly bulk leaf carbon isotopic composition varied from -34.5 % in P. ponderosa to -24.7 % in P. lambertiana and became more depleted in 13C from the spring to the summer. Mean monthly leaf sugar varied from -29.3 % in P. ponderosa to -21.8 % in P. lambertiana and was enriched in 13C during the winter, spring and autumn, but depleted during the mid-summer. Leaf water hydrogen isotopic composition was 28.4 to 68.8 % more enriched in deuterium than source water and this enrichment was greater as seasonal drought progressed. These data indicate that leaf carbon and leaf water hydrogen isotopic composition provide sensitive measures that connect plant physiological processes to short-term climatic variability.

Isotopic composition of atmospheric moisture from pan water evaporation measurements.

PubMed

Devi, Pooja; Jain, Ashok Kumar; Rao, M Someshwer; Kumar, Bhishm

2015-01-01

A continuous and reliable time series data of the stable isotopic composition of atmospheric moisture is an important requirement for the wider applicability of isotope mass balance methods in atmospheric and water balance studies. This requires routine sampling of atmospheric moisture by an appropriate technique and analysis of moisture for its isotopic composition. We have, therefore, used a much simpler method based on an isotope mass balance approach to derive the isotopic composition of atmospheric moisture using a class-A drying evaporation pan. We have carried out the study by collecting water samples from a class-A drying evaporation pan and also by collecting atmospheric moisture using the cryogenic trap method at the National Institute of Hydrology, Roorkee, India, during a pre-monsoon period. We compared the isotopic composition of atmospheric moisture obtained by using the class-A drying evaporation pan method with the cryogenic trap method. The results obtained from the evaporation pan water compare well with the cryogenic based method. Thus, the study establishes a cost-effective means of maintaining time series data of the isotopic composition of atmospheric moisture at meteorological observatories. The conclusions drawn in the present study are based on experiments conducted at Roorkee, India, and may be examined at other regions for its general applicability.

Stable Isotope Systematics in Grasshopper Assemblages Along an Elevation Gradient, Colorado

NASA Astrophysics Data System (ADS)

Kohn, M. J.; Evans, S.; Dean, J.; Nufio, C.

2012-12-01

Insects comprise over three quarters of all animal species, yet studies of body water isotopic composition are limited to only the cockroach, the hoverfly, and chironomid flies. These studies suggest that oxygen and hydrogen isotopic compositions in body water are primarily controlled by dietary water sources, with modification from respiratory and metabolic processes. In particular, outward diffusion of isotopically depleted water vapor through insect spiracles at low humidity enriches residual body water in 18O and 2H (D). Stable isotope compositions (δ18O and δD) also respond to gradients in elevation and humidity, but these influences remain poorly understood. In this study, we measured grasshopper body water and local vegetation isotopic compositions along an elevation gradient in Colorado to evaluate three hypotheses: 1) Insect body water isotopic composition is directly related to food source water composition 2) Water vapor transport alters body water isotopic compositions relative to original diet sources, and 3) Elevation gradients influence isotopic compositions in insect body water. Thirty-five species of grasshopper were collected from 14 locations in Colorado grasslands, ranging in elevation from 450 to 800 meters (n=131). Body water was distilled from previously frozen grasshopper specimens using a vacuum extraction line, furnaces (90 °C), and liquid nitrogen traps. Water samples were then analyzed for δ18O and δD on an LGR Liquid Water Isotope Analyzer, housed in the Department of Geosciences, Boise State University. Grasshopper body water isotopic compositions show wide variation, with values ranging between -76.64‰ to +42.82‰ in δD and -3.06‰ to +26.78‰ in δ18O. Precipitation δ18O values over the entire Earth excluding the poles vary by approximately 30‰, comparable to the total range measured in our single study area. Most grasshopper values deviate from the global meteoric water line relating δ18O and δD in precipitation, consistent with evaporative enrichment in food (plants) due to plant transpiration. However, grasshopper body water from any given location is further enriched in 18O and D relative to food. Isotopic values decrease slightly with increasing elevation, but some specific grasshopper species appear more sensitive to elevation. Overall, evaporative enrichment of 18O and D in this relatively dry environment appears the strongest factors influencing grasshopper compositions.

Multiscale Modeling of Novel Carbon Nanotube/Copper-Composite Material Used in Microelectronics

NASA Astrophysics Data System (ADS)

Awad, Ibrahim; Ladani, Leila

2016-06-01

Current carrying capacity is one of the elements that hinders further miniaturization of Copper (Cu) interconnects. Therefore, there is a need to propose new materials with higher ampacity (current carrying capacity) that have the potential to replace Cu. Experimental observations have shown that Carbon Nanotube (CNT)/Cu-composite material has a hundredfold ampacity of Cu, which makes it a good candidate to replace Cu. However, sufficient information about the mechanical behavior of the novel CNT/Cu-composite is not available. In the current paper, the CNT/Cu-composite is utilized to construct Through Silicon Via (TSV). The mechanical behavior, specifically the fatigue life, of the CNT/Cu-TSV is evaluated by applying a multiscale modeling approach. Molecular Dynamics (MD) simulations are conducted to evaluate the tensile strength and the coefficient of thermal expansion of CNTs. MD simulation is also used to determine the interface behavior between CNTs and Cu. MD simulation results are integrated into Finite Element analysis at the micro-level to estimate the fatigue life of the CNT/Cu-TSV. A comparison is made with base material; Cu. CNTs addition has redistributed the plastic deformation in Cu to occur at two different locations (Si/Cu interface and Cu/CNT interface) instead of only one location (Si/Cu interface) in the case of Cu-only-TSV. Thus, the maximum equivalent plastic strain has been alleviated in the CNT/Cu-TSV. Accordingly, CNT/Cu-TSV has shown a threefold increase in the fatigue life. This is a solid indication of the improvement in the fatigue life that is attributed to the addition of CNTs.

Preparation and characterization of polyaniline-copper composites by electrical explosion of wire.

PubMed

Liu, Aijie; Bac, Luong Huu; Kim, Jin-Chun; Liu, Lizhu

2012-07-01

Polyaniline-copper composites with a polyacrylic acid (PAA) were synthesized by electrical explosion of wire. Polyaniline (PANI) and PAA were put into the explosion medium, deionized water (DIW) and ethanol, stirred for 24 hrs and sonicated for 2 hrs. These solutions were used as base liquids for explosion process to fabricate Cu nanoparticle. Optical absorption in the UV-visible region of PANI and PANI/PAA-Cu composites was measured in a range of 200-900 nm. X-ray diffraction was used to analyze the phase of the composites. XRD pattern showed the PANI was amorphous and copper was polycrystalline. Two phases of Cu and Cu2O were formed in aqueous solution while single Cu phase was obtained in ethanol solution. Field emission scanning electron microscope was used to observe the microstructure of the composites. The synthesized composites were extensively characterized by Fourier Transform Infrared (FTIR) spectroscopy and electrical measurements.

Nitrogen Isotope Evidence for a Shift in Eastern Beringian Nitrogen Cycle after the Terminal Pleistocene

NASA Astrophysics Data System (ADS)

Tahmasebi, F.; Longstaffe, F. J.; Zazula, G.

2016-12-01

The loess deposits of eastern Beringia, a region in North America between 60° and 70°N latitude and bounded by Chukchi Sea to the west and the Mackenzie River to the east, are a magnificent repository of Late Pleistocene megafauna fossils. The stable carbon and nitrogen isotope compositions of these fossils are measured to determine the paleodiet of these animals, and hence the paleoenvironment of this ecosystem during the Quaternary. For this approach to be most successful, however, requires consideration of possible changes in nutrient cycling and hence the carbon and nitrogen isotopic compositions of vegetation in this ecosystem. To test for such a shift following the terminal Pleistocene, we analyzed the stable carbon and nitrogen isotope compositions of modern plants and bone collagen of Arctic ground squirrels from Yukon Territory, and fossil plants and bones recovered from Late Pleistocene fossil Arctic ground squirrel nests. The data for modern samples provided a measure of the isotopic fractionation between ground squirrel bone collagen and their diet. The over-wintering isotopic effect of decay on typical forage grasses was also measured to evaluate its role in determining fossil plant isotopic compositions. The grasses showed only a minor change ( 0-1 ‰) in carbon isotope composition, but a major change ( 2-10 ‰) in nitrogen isotope composition over the 317-day experiment. Based on the modern carbon isotope fractionation between ground squirrel bone collagen and their diet, the modern vegetation carbon isotopic baseline provides a suitable proxy for the Late Pleistocene of eastern Beringia, after accounting for the Suess effect. However, the predicted nitrogen isotope composition of vegetation comprising the diet of fossil ground squirrels remains 2.5 ‰ higher than modern grasslands in this area, even after accounting for possible N-15 enrichment during decay. This result suggests a change in N cycling in this region since the Late Pleistocene.

Thallium isotope composition of the upper continental crust and rivers - An investigation of the continental sources of dissolved marine thallium

USGS Publications Warehouse

Nielsen, S.G.; Rehkamper, M.; Porcelli, D.; Andersson, P.; Halliday, A.N.; Swarzenski, P.W.; Latkoczy, C.; Gunther, D.

2005-01-01

The thallium (Tl) concentrations and isotope compositions of various river and estuarine waters, suspended riverine particulates and loess have been determined. These data are used to evaluate whether weathering reactions are associated with significant Tl isotope fractionation and to estimate the average Tl isotope composition of the upper continental crust as well as the mean Tl concentration and isotope composition of river water. Such parameters provide key constraints on the dissolved Tl fluxes to the oceans from rivers and mineral aerosols. The Tl isotope data for loess and suspended riverine detritus are relatively uniform with a mean of ??205Tl = -2.0 ?? 0.3 (??205Tl represents the deviation of the 205Tl/203Tl isotope ratio of a sample from NIST SRM 997 Tl in parts per 104). For waters from four major and eight smaller rivers, the majority were found to have Tl concentrations between 1 and 7 ng/kg. Most have Tl isotope compositions very similar (within ??1.5 ??205Tl) to that deduced for the upper continental crust, which indicates that no significant Tl isotope fractionation occurs during weathering. Based on these results, it is estimated that rivers have a mean natural Tl concentration and isotope composition of 6 ?? 4 ng/kg and ??205Tl = -2.5 ?? 1.0, respectively. In the Amazon estuary, both additions and losses of Tl were observed, and these correlate with variations in Fe and Mn contents. The changes in Tl concentrations have much lower amplitudes, however, and are not associated with significant Tl isotope effects. In the Kalix estuary, the Tl concentrations and isotope compositions can be explained by two-component mixing between river water and a high-salinity end member that is enriched in Tl relative to seawater. These results indicate that Tl can display variable behavior in estuarine systems but large additions and losses of Tl were not observed in the present study. Copyright ?? 2005 Elsevier Ltd.

Deciphering the iron isotope message of the human body

NASA Astrophysics Data System (ADS)

Walczyk, Thomas; von Blanckenburg, Friedhelm

2005-04-01

Mass-dependent variations in isotopic composition are known since decades for the light elements such as hydrogen, carbon or oxygen. Multicollector-inductively coupled plasma mass spectrometry (MC-ICP-MS) and double-spike thermal ionization mass spectrometry (TIMS) permit us now to resolve small variations in isotopic composition even for the heavier elements such as iron. Recent studies on the iron isotopic composition of human blood and dietary iron sources have shown that lighter iron isotopes are enriched along the food chain and that each individual bears a certain iron isotopic signature in blood. To make use of this finding in biomedical research, underlying mechanisms of isotope fractionation by the human body need to be understood. In this paper available iron isotope data for biological samples are discussed within the context of isotope fractionation concepts and fundamental aspects of human iron metabolism. This includes evaluation of new data for body tissues which show that blood and muscle tissue have a similar iron isotopic composition while heavier iron isotopes are concentrated in the liver. This new observation is in agreement with our earlier hypothesis of a preferential absorption of lighter iron isotopes by the human body. Possible mechanisms for inducing an iron isotope effect at the cellular and molecular level during iron uptake are presented and the potential of iron isotope effects in human blood as a long-term measure of dietary iron absorption is discussed.

Morphological Control of Mesoporosity and Nanoparticles within Co3O4-CuO Electrospun Nanofibers: Quantum Confinement and Visible Light Photocatalysis Performance.

PubMed

Pradhan, Amaresh C; Uyar, Tamer

2017-10-18

The one-dimensional (1D) mesoporous and interconnected nanoparticles (NPs) enriched composite Co 3 O 4 -CuO nanofibers (NFs) in the ratio Co:Cu = 1/4 (Co 3 O 4 -CuO NFs) composite have been synthesized by electrospinning and calcination of mixed polymeric template. Not merely the mesoporous composite Co 3 O 4 -CuO NFs but also single mesoporous Co 3 O 4 NFs and CuO NFs have been produced for comparison. The choice of mixed polymer templates such as polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG) for electrospinning is responsible for the formation of 1D mesoporous NFs. The HR-TEM result showed evolution of interconnected nanoparticles (NPs) and creation of mesoporosity in all electrospun NFs. The quantum confinement is due to NPs within NFs and has been proved by the surface-enhanced Raman scattering (SERS) study and the UV-vis-NRI diffuse reflectance spectra (DRS). The high intense photoluminescence (PL) spectra showing blue shift of all NFs also confirmed the quantum confinement phenomena. The lowering of PL spectrum after mixing of CuO in Co 3 O 4 nanofibers framework (Co 3 O 4 -CuO NFs) proved CuO as an efficient visible light response low cost cocatalyst/charge separator. The red shifting of the band gap in composite Co 3 O 4 -CuO NFs is due to the internal charge transfer between Co 2+ to Co 3+ and Cu 2+ , proved by UV-vis absorption spectroscopy. Creation of oxygen vacancies by mixing of CuO and Co 3 O 4 also prevents the electron-hole recombination and enhances the photocatalytic activity in composite Co 3 O 4 -CuO NFs. The photocurrent density, Mott-Schottky (MS), and electrochemical impedance spectroscopy (EIS) studies of all NFs favor the high photocatalytic performance. The mesoporous composite Co 3 O 4 -CuO NFs exhibits high photocatalytic activity toward phenolic compounds degradation as compared to the other two NFs (Co 3 O 4 NFs and CuO NFs). The kinetic study of phenolic compounds followed first order rate equation. The high photocatalytic activity of composite Co 3 O 4 -CuO NFs is attributed to the formation of mesoporosity and interconnected NPs within NFs framework, quantum confinement, extended light absorption property, internal charge transfer, and effective photogenerated charge separations.

Cu2O/CuO Bilayered Composite as a High-Efficiency Photocathode for Photoelectrochemical Hydrogen Evolution Reaction

NASA Astrophysics Data System (ADS)

Yang, Yang; Xu, Di; Wu, Qingyong; Diao, Peng

2016-10-01

Solar powered hydrogen evolution reaction (HER) is one of the key reactions in solar-to-chemical energy conversion. It is desirable to develop photocathodic materials that exhibit high activity toward photoelectrochemical (PEC) HER at more positive potentials because a higher potential means a lower overpotential for HER. In this work, the Cu2O/CuO bilayered composites were prepared by a facile method that involved an electrodeposition and a subsequent thermal oxidation. The resulting Cu2O/CuO bilayered composites exhibited a surprisingly high activity and good stability toward PEC HER, expecially at high potentials in alkaline solution. The photocurrent density for HER was 3.15 mA·cm-2 at the potential of 0.40 V vs. RHE, which was one of the two highest reported at the same potential on copper-oxide-based photocathode. The high photoactivity of the bilayered composite was ascribed to the following three advantages of the Cu2O/CuO heterojunction: (1) the broadened light absorption band that made more efficient use of solar energy, (2) the large space-charge-region potential that enabled a high efficiency for electron-hole separation, and (3) the high majority carrier density that ensured a faster charge transportation rate. This work reveals the potential of the Cu2O/CuO bilayered composite as a promising photocathodic material for solar water splitting.

The 68mCu/68Cu isotope as a new probe for hyperfine studies: The nuclear moments

NASA Astrophysics Data System (ADS)

Fenta, A. S.; Pallada, S.; Correia, J. G.; Stachura, M.; Johnston, K.; Gottberg, A.; Mokhles Gerami, A.; Röder, J.; Grawe, H.; Brown, B. A.; Köster, U.; Mendonça, T. M.; Ramos, J. P.; Marsh, B. A.; Day Goodacre, T.; Amaral, V. S.; Pereira, L. M. C.; Borge, M. J. G.; Haas, H.

2016-09-01

Time Differential Perturbed Angular Correlation of γ-rays (TDPAC) experiments were performed for the first time in the decay of 68m Cu (6-, 721 \\text{keV}, 3.75 \\text{min}) produced at the ISOLDE facility at CERN. Due to the short half-life of the source isotope, the measurements were carried out online. The intermediate state (2+, 84.1 \\text{keV}, 7.84 \\text{ns}) offers the unique opportunity to study the electromagnetic fields acting at a copper probe in condensed matter via hyperfine interactions. The present work allowed determination of the nuclear moments for this state. The electric quadrupole moment |Q(2+,84.1 \\text{keV})|=0.110(3) \\text{b} was obtained from an experiment performed in Cu2O and the magnetic dipole moment |μ|=2.857(6) μ_\\text{N} from measurements in cobalt and nickel foils. The results are discussed in the framework of shell model calculations and the additivity rule for nuclear moments with respect to the robustness of the N = 40 sub-shell.

Tooth enamel maturation reequilibrates oxygen isotope compositions and supports simple sampling methods

NASA Astrophysics Data System (ADS)

Trayler, Robin B.; Kohn, Matthew J.

2017-02-01

Oxygen isotope and major element zoning patterns of several disparate ungulate teeth were collected to evaluate the timing and geometry of enamel formation, records of isotope zoning, and tooth enamel sampling strategies. Isotopic zoning in mammalian tooth enamel encodes a sub-annual time series of isotopic variation of an animal's body water composition, with a damping factor that depends on the specifics of how enamel mineralizes. Enamel formation comprises two stages: precipitation of appositional enamel with a high CO3:PO4 ratio, followed by precipitation of maturational enamel with a lower CO3:PO4. If appositional and maturational enamel both contribute to isotope compositions (but with different CO3:PO4), and if isotope compositions vary seasonally, paired δ18O values from CO3 and PO4 profiles should show a spatial separation. CO3 isotope patterns should be shifted earlier seasonally than PO4 isotope patterns. Such paired profiles for new and published data show no resolvable shifts, i.e. CO3 and PO4 δ18O profiles show coincident maxima and minima. This coincidence suggests that enamel maturation reequilibrates appositional isotope compositions. If enamel maturation establishes enamel isotope compositions, the geometry of maturation, not apposition, should be considered when devising sampling protocols. X-ray maps of Ca zoning show that the majority of enamel (inner and middle layers) mineralizes heavily at a high angle to the external tooth surface and the enamel-dentine junction over length scales of 2-4 mm, while the outer enamel surface mineralizes more slowly. These data suggest that isotopic sampling strategies should parallel maturational geometry and focus on interior enamel to improve data fidelity. The magnitude of isotopic damping is also smaller than implied in previous studies, so tooth enamel zoning more closely reflects original body water isotopic variations than previously assumed.

Lead isotope compositions of Late Cretaceous and early Tertiary igneous rocks and sulfide minerals in Arizona: Implications for the sources of plutons and metals in porphyry copper deposits

USGS Publications Warehouse

Bouse, R.M.; Ruiz, J.; Titley, S.R.; Tosdal, R.M.; Wooden, J.L.

1999-01-01

Porphyry copper deposits in Arizona are genetically associated with Late Cretaceous and early Tertiary igneous complexes that consist of older intermediate volcanic rocks and younger intermediate to felsic intrusions. The igneous complexes and their associated porphyry copper deposits were emplaced into an Early Proterozoic basement characterized by different rocks, geologic histories, and isotopic compositions. Lead isotope compositions of the Proterozoic basement rocks define, from northwest to southeast, the Mojave, central Arizona, and southeastern Arizona provinces. Porphyry copper deposits are present in each Pb isotope province. Lead isotope compositions of Late Cretaceous and early Tertiary plutons, together with those of sulfide minerals in porphyry copper deposits and of Proterozoic country rocks, place important constraints on genesis of the magmatic suites and the porphyry copper deposits themselves. The range of age-corrected Pb isotope compositions of plutons in 12 Late Cretaceous and early Tertiary igneous complexes is 206Pb/204Pb = 17.34 to 22.66, 207Pb/204Pb = 15.43 to 15.96, and 208Pb/204Pb = 37.19 to 40.33. These Pb isotope compositions and calculated model Th/U are similar to those of the Proterozoic rocks in which the plutons were emplaced, thereby indicating that Pb in the younger rocks and ore deposits was inherited from the basement rocks and their sources. No Pb isotope differences distinguish Late Cretaceous and early Tertiary igneous complexes that contain large economic porphyry copper deposits from less rich or smaller deposits that have not been considered economic for mining. Lead isotope compositions of Late Cretaceous and early Tertiary plutons and sulfide minerals from 30 metallic mineral districts, furthermore, require that the southeastern Arizona Pb province be divided into two subprovinces. The northern subprovince has generally lower 206Pb/204Pb and higher model Th/U, and the southern subprovince has higher 206Pb/204Pb and lower model Th/U. These Pb isotope differences are inferred to result from differences in their respective post-1.7 Ga magmatic histories. Throughout Arizona, Pb isotope compositions of Late Cretaceous and early Tertiary plutons and associated sulfide minerals are distinct from those of Jurassic plutons and also middle Tertiary igneous rocks and sulfide minerals. These differences most likely reflect changes in tectonic setting and magmatic sources. Within Late Cretaceous and early Tertiary igneous complexes that host economic porphyry copper deposits, there is commonly a decrease in Pb isotope composition from older to younger plutons. This decrease in Pb isotope values with time suggests an increasing involvement of crust with lower U/Pb than average crust in the source(s) of Late Cretaceous and early Tertiary magmas. Lead isotope compositions of the youngest porphyries in the igneous complexes are similar to those in most sulfide minerals within the associated porphyry copper deposit. This Pb isotope similarity argues for a genetic link between them. However, not all Pb in the sulfide minerals in porphyry copper deposits is magmatically derived. Some sulfide minerals, particularly those that are late stage, or distal to the main orebody, or in Proterozoic or Paleozoic rocks, have elevated Pb isotope compositions displaced toward the gross average Pb isotope composition of the local country rocks. The more radiogenic isotopic compositions argue for a contribution of Pb from those rocks at the site of ore deposition. Combining the Pb isotope data with available geochemical, isotopic, and petrologic data suggests derivation of the young porphyry copper-related plutons, most of their Pb, and other metals from a hybridized lower continental crustal source. Because of the likely involvement of subduction-related mantle-derived basaltic magma in the hybridized lower crustal source, an indiscernible mantle contribution is probable in the porphyry magmas. Clearly, in addition

Isotopic Compositions of the Elements, 2001

NASA Astrophysics Data System (ADS)

Böhlke, J. K.; de Laeter, J. R.; De Bièvre, P.; Hidaka, H.; Peiser, H. S.; Rosman, K. J. R.; Taylor, P. D. P.

2005-03-01

The Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry completed its last review of the isotopic compositions of the elements as determined by isotope-ratio mass spectrometry in 2001. That review involved a critical evaluation of the published literature, element by element, and forms the basis of the table of the isotopic compositions of the elements (TICE) presented here. For each element, TICE includes evaluated data from the "best measurement" of the isotope abundances in a single sample, along with a set of representative isotope abundances and uncertainties that accommodate known variations in normal terrestrial materials. The representative isotope abundances and uncertainties generally are consistent with the standard atomic weight of the element Ar(E) and its uncertainty U[Ar(E)] recommended by CAWIA in 2001.

Atomistic models of Cu diffusion in CuInSe2 under variations in composition

NASA Astrophysics Data System (ADS)

Sommer, David E.; Dunham, Scott T.

2018-03-01

We construct an analytic model for the composition dependence of the vacancy-mediated Cu diffusion coefficient in undoped CuInSe2 using parameters from density functional theory. The applicability of this model is supported numerically with kinetic lattice Monte Carlo and Onsager transport tensors. We discuss how this model relates to experimental measurements of Cu diffusion, arguing that our results can account for significant contributions to the bulk diffusion of Cu tracers in non-stoichiometric CuInSe2.

Inductively coupled plasma-mass spectrometric method for the determination of dissolved trace elements in natural water

USGS Publications Warehouse

Garbarino, J.R.; Taylor, Howard E.

1996-01-01

An inductively coupled plasma-mass spectrometry method was developed for the determination of dissolved Al, As, B, Ba, Be, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Sr, Tl, U, V, and Zn in natural waters. Detection limits are generally in the 50-100 picogram per milliliter (pg/mL) range, with the exception of As which is in the 1 microgram per liter (ug/L) range. Interferences associated with spectral overlap from concomitant isotopes or molecular ions and sample matrix composition have been identified. Procedures for interference correction and reduction related to isotope selection, instrumental operating conditions, and mathematical data processing techniques are described. Internal standards are used to minimize instrumental drift. The average analytical precision attainable for 5 times the detection limit is about 16 percent. The accuracy of the method was tested using a series of U.S. Geological Survey Standard Reference Water Standards (SWRS), National Research Council Canada Riverine Water Standard, and National Institute of Standards and Technology (NIST) Trace Elements in Water Standards. Average accuracies range from 90 to 110 percent of the published mean values.

Anthropogenic versus natural control on trace element and Sr-Nd-Pb isotope stratigraphy in peat sediments of southeast Florida (USA), ˜1500 AD to present

NASA Astrophysics Data System (ADS)

Kamenov, George D.; Brenner, Mark; Tucker, Jaimie L.

2009-06-01

Analysis of a well-dated peat core from Blue Cypress Marsh (BCM) provides a detailed record of natural and anthropogenic factors that controlled the geochemical cycles of a number of trace elements in Florida over the last five centuries. The trace elements were divided into "natural" and "anthropogenic" groups using concentration trends from the bottom to the top of the core. The "natural" group includes Li, Sc, Cr, Co, Ga, Ge, Zr, Nb, Cs, Ba, Hf, Y, Ta, Th, and REE (Rare Earth Elements). These elements show similar concentrations throughout the core, indicating that changes in human activities after European arrival in the "New World" did not affect their geochemical cycles. The "anthropogenic" group includes Pb, Cu, Zn, V, Sb, Sn, Bi, and Cd. Upcore enrichment of these elements indicates enhancement by anthropogenic activities. From the early 1500s to present, fluxes of the "anthropogenic" metals to the marsh increased significantly, with modern accumulation rates several-fold (e.g., V) to hundreds of times (e.g., Zn) greater than pre-colonial rates. The dominant input mechanism for trace elements from both groups to the marsh has been atmospheric deposition. Atmospheric input of a number of the elements, including the anthropogenic metals, was dominated by local sources during the last century. For several elements, long-distant transport may be important. For instance, REE and Nd isotopes provide evidence for long-range atmospheric transport dominated by Saharan dust. The greatest increase in flux of the "anthropogenic" metals occurred during the 20th century and was caused by changes in the chemical composition of atmospheric deposition entering the marsh. Increased atmospheric inputs were a consequence of several anthropogenic activities, including fossil fuel combustion (coal and oil), agricultural activities, and quarrying and mining operations. Pb and V exhibit similar trends, with peak accumulation rates in 1970. The principal anthropogenic source of V is oil combustion. The decline in V accumulation after 1970 in the BCM peat corresponds to the introduction of low-sulfur fuels and the change from heavy to distilled oils since the 1970s. After the 1920s, Pb distribution in the peat follows closely the history of alkyl lead consumption in the US, which peaked in the 1970s. Pb isotopes support this inference and furthermore, record changes in the ore sources used to produce leaded gasoline. Idaho ores dominated the peat Pb isotope record until the 1960s, followed by Pb from Mississippi Valley Type deposits from the 1960s to the 1980s. Enhanced fluxes of Cu, Zn, Cd, Sn, Sb, Bi, and to some extent Ni during the last century are likely also related to fossil fuel combustion. Local agricultural activities may also have influenced the geochemical cycles of Cu and Zn. The peat record shows enhanced U accumulation during the last century, possibly related to phosphate mining in western Florida. Sr isotopes in the peat core also reflect anthropogenic influence. The 87Sr/ 86Sr ratio decreases from natural background values in the basal part of the core to lower values in the upper part of the core. The Sr isotope shift is probably related to quarrying operations in Florida, and marks the first time an anthropogenic signal has been detected using the Sr isotope record in a peat core.

Routine production of copper-64 using 11.7MeV protons

NASA Astrophysics Data System (ADS)

Jeffery, C. M.; Smith, S. V.; Asad, A. H.; Chan, S.; Price, R. I.

2012-12-01

Reliable production of copper-64 (64Cu) was achieved by irradiating enriched nickel-64 (64Ni, >94.8%) in an IBA 18/9 cyclotron. Nickel-64 (19.1 ± 3.0 mg) was electroplated onto an Au disc (125μm × 15mm). Targets were irradiated with 11.7 MeV protons for 2 hours at 40μA. Copper isotopes (60,61,62,64Cu) were separated from target nickel and cobalt isotopes (55,57,61Co) using a single ion exchange column, eluted with varying concentration of low HCl alcohol solutions. The 64Ni target material was recovered and reused. The 64Cu production rate was 1.46±0.3MBq/μA.hr/mg64Ni(n = 10) (with a maximum of 2.6GBq of 64Cu isolated after 2hr irradiation at 40uA. Radionuclidic purity of the 64Cu was 98.7 ± 1.6 % at end of separation. Cu content was < 6mg/L (n = 21). The specific activity of 64Cu was determined by ICP-MS and by titration with Diamsar to be 28.9±13.0GBq/μmol[0.70±0.35Ci/μmol]/(μA.hr/mg64Ni)(n = 10) and 13.1±12.0GBq/μmol[0.35±0.32Ci/μmol]/(μA.hr/mg64Ni)(n = 9), respectively; which are in agreement, however, further work is required.

Formation of the Vysoká-Zlatno Cu-Au skarn-porphyry deposit, Slovakia

NASA Astrophysics Data System (ADS)

Koděra, Peter; Lexa, Jaroslav; Fallick, Anthony E.

2010-12-01

The central zone of the Miocene Štiavnica stratovolcano hosts several occurrences of Cu-Au skarn-porphyry mineralisation, related to granodiorite/quartz-diorite porphyry dyke clusters and stocks. Vysoká-Zlatno is the largest deposit (13.4 Mt at 0.52% Cu), with mineralised Mg-Ca exo- and endoskarns, developed at the prevolcanic basement level. The alteration pattern includes an internal K- and Na-Ca silicate zone, surrounded by phyllic and argillic zones, laterally grading into a propylitic zone. Fluid inclusions in quartz veinlets in the internal zone contain mostly saline brines with 31-70 wt.% NaCl eq. and temperatures of liquid-vapour homogenization (Th) of 186-575°C, indicating fluid heterogenisation. Garnet contains inclusions of variable salinity with 1-31 wt.% NaCl eq. and Th of 320-360°C. Quartz-chalcopyrite veinlets host mostly low-salinity fluid inclusions with 0-3 wt.% NaCl eq. and Th of 323-364°C. Data from sphalerite from the margin of the system indicate mixing with dilute and cooler fluids. The isotopic composition of fluids in equilibrium with K-alteration and most skarn minerals (both prograde and retrograde) indicates predominantly a magmatic origin (δ18Ofluid 2.5-12.3‰) with a minor meteoric component. Corresponding low δDfluid values are probably related to isotopic fractionation during exsolution of the fluid from crystallising magma in an open system. The data suggest the general pattern of a distant source of magmatic fluids that ascended above a zone of hydraulic fracturing below the temperature of ductile-brittle transition. The magma chamber at ˜5-6 km depth exsolved single-phase fluids, whose properties were controlled by changing PT conditions along their fluid paths. During early stages, ascending fluids display liquid-vapour immiscibility, followed by physical separation of both phases. Low-salinity liquid associated with ore veinlets probably represents a single-phase magmatic fluid/magmatic vapour which contracted into liquid upon its ascent.

Copper-nickel-rich, amalgamated ferromanganese crust-nodule deposits from Shatsky Rise, NW Pacific

USGS Publications Warehouse

Hein, J.R.; Conrad, T.A.; Frank, M.; Christl, M.; Sager, W.W.

2012-01-01

A unique set of ferromanganese crusts and nodules collected from Shatsky Rise (SR), NW Pacific, were analyzed for mineralogical and chemical compositions, and dated using Be isotopes and cobalt chronometry. The composition of these midlatitude, deep-water deposits is markedly different from northwest-equatorial Pacific (PCZ) crusts, where most studies have been conducted. Crusts and nodules on SR formed in close proximity and some nodule deposits were cemented and overgrown by crusts, forming amalgamated deposits. The deep-water SR crusts are high in Cu, Li, and Th and low in Co, Te, and Tl concentrations compared to PCZ crusts. Thorium concentrations (ppm) are especially striking with a high of 152 (mean 56), compared to PCZ crusts (mean 11). The deep-water SR crusts show a diagenetic chemical signal, but not a diagenetic mineralogy, which together constrain the redox conditions to early oxic diagenesis. Diagenetic input to crusts is rare, but unequivocal in these deep-water crusts. Copper, Ni, and Li are strongly enriched in SR deep-water deposits, but only in layers older than about 3.4 Ma. Diagenetic reactions in the sediment and dissolution of biogenic calcite in the water column are the likely sources of these metals. The highest concentrations of Li are in crust layers that formed near the calcite compensation depth. The onset of Ni, Cu, and Li enrichment in the middle Miocene and cessation at about 3.4 Ma were accompanied by changes in the deep-water environment, especially composition and flow rates of water masses, and location of the carbonate compensation depth.

Constraints on the origin of adakites and porphyry Cu-Mo mineralization in Chongjiang, Southern Gangdese, the Tibetan Plateau

NASA Astrophysics Data System (ADS)

Hu, Yong-bin; Liu, Ji-qiang; Ling, Ming-xing; Liu, Yan; Ding, Xing; Liu, Dun-yi; Sun, Wei-dong

2017-11-01

Chongjiang is a low-grade porphyry Cu deposit, located in the Gangdese belt, south Tibet. The petrogenesis and geodynamic settings of the Miocene intrusions associated with the deposit remain controversial. This study presents new results on in situ zircon Hf-O isotopic compositions and U-Pb ages, whole rock major and trace elements, and Sr-Nd isotopes for the adakitic intrusions from Chongjiang deposit. The ore-bearing biotite monzogranite porphyry has adakitic characteristics, with enriched large-ion-lithophile elements (LILE) and light rare earth elements (LREE), and depleted in high-field-strength elements (HFSE), P and Ti. LA-ICP-MS zircon U-Pb dating indicates that the ore-bearing and barren adakites were emplaced at 14.9 ± 0.3 Ma and 12.9 ± 0.3 Ma, respectively. The porphyry is characterized by relatively high initial 87Sr/86Sr ratios (0.7059 to 0.7066), and negative whole-rock εNd(t) values (- 3.8 to - 2.6). Zircon δ18O is slightly higher than mantle values (5.0 to 7.2‰), with varied εHf(t) (- 1.0 to 7.6). Most of the in situ zircon Hf-O isotopic data plot in a binary mixing trend between MORB and lower continental crust-derived melts. These results indicate contributions from mixing of a mantle-like source (e.g., slab melts) with continental crust. Interestingly, most of the samples plot in the field defined by Dabie adakites (representing partial melting of the lower continental crust), with several samples near/in the circum-Pacific adakite field (representing partial melting of subducted oceanic slabs), which seemingly indicates that Chongjiang adakites mostly formed through partial melting of lower continental crust, with a small amount derived from oceanic slab melts. These may be plausibly explained by plagioclase retention in the thickened Tibetan continental crust, which lowers Sr contents in the magmas during crustal assimilation. Such a model is supported by other adakite discrimination diagrams, which all point towards slab melting. Crustal contamination can compellingly explain the low grade of the Chongjiang deposit. Considering the temporal-spatial distribution of porphyry Cu deposits, geochemical characteristics and high oxygen fugacity, we propose that the subducting Ninetyeast Ridge probably played a critical role in controlling the formation of Miocene adakites and porphyry copper deposits in the eastern Gangdese belt.

Origin of the Wunugetushan porphyry Cu-Mo deposit, Inner Mongolia, NE China: Constraints from geology, geochronology, geochemistry, and isotopic compositions

NASA Astrophysics Data System (ADS)

Zhang, Fang-Fang; Wang, Yin-Hong; Liu, Jia-Jun; Wang, Jian-Ping; Zhao, Chun-Bo; Song, Zhi-Wei

2016-03-01

The Wunugetushan porphyry Cu-Mo deposit is located in the southeastern margin of the Mongol-Okhotsk Orogenic Belt and in the northwestern segment of the Great Xing'an Range, NE China. The orebodies of this deposit are mainly hosted in the monzogranitic porphyry stock and in contact with the granitic porphyry dyke and biotite granite batholith. The SHRIMP zircon U-Pb dating of the granitic porphyry dyke yielded ages of 201.4 ± 3.1 Ma (2σ, MSWD = 1.5). These results indicate that the magmatism in the Wunugetushan area might have occurred at ca. 201 Ma in the early Jurassic, and that the mineralization age (ca. 181 Ma) of this deposit is later than the age of intrusive granitic porphyry in the area. Geochemically, the Wunugetushan granitoids belong to high-K calc-alkaline and shoshonitic series, enriched in K, Rb, Nd, and Pb, and depleted in Sr, Nb, Ti and P, with negative Eu anomalies. In situ Hf isotopic analyses of zircons using LA-MC-ICP-MS indicate that the εHf(t) values for zircons from a granitic porphyry sample vary from +2.4 to +11.8 and that the corresponding crustal model ages (TDMC) vary from 483 to 1088 Ma. The least-altered monzogranitic porphyry, granitic porphyry and biotite granite yielded relatively uniform εNd(t) values from -1.0 to +0.6 and low (87Sr/86Sr)i ratios ranging from 0.704387 to 0.708385. The geochemical and Sr-Nd-Hf isotopic data for the granitoids indicate that the source magma for these rocks could be derived from a juvenile lower crust. The δ34S values of sulfides show a narrow range (+0.76‰ to +3.20‰) similar to those of magmatic sulfur, further implying a lower crust origin. Based on the results of this study and the regional geodynamic evolution, it is proposed that the formation of the Wunugetushan deposit and associated granitoids should be linked to the southeastward subduction of the Mongol-Okhotsk oceanic plate beneath the Erguna Massif during the early Jurassic, and that the monzogranitic porphyry intrusions in Wunugetushan area probably provided important ore metals responsible for the large-scale Cu-Mo mineralization.

Automated Sample Preparation for Radiogenic and Non-Traditional Metal Isotopes: Removing an Analytical Barrier for High Sample Throughput

NASA Astrophysics Data System (ADS)

Field, M. Paul; Romaniello, Stephen; Gordon, Gwyneth W.; Anbar, Ariel D.; Herrmann, Achim; Martinez-Boti, Miguel A.; Anagnostou, Eleni; Foster, Gavin L.

2014-05-01

MC-ICP-MS has dramatically improved the analytical throughput for high-precision radiogenic and non-traditional isotope ratio measurements, compared to TIMS. The generation of large data sets, however, remains hampered by tedious manual drip chromatography required for sample purification. A new, automated chromatography system reduces the laboratory bottle neck and expands the utility of high-precision isotope analyses in applications where large data sets are required: geochemistry, forensic anthropology, nuclear forensics, medical research and food authentication. We have developed protocols to automate ion exchange purification for several isotopic systems (B, Ca, Fe, Cu, Zn, Sr, Cd, Pb and U) using the new prepFAST-MC™ (ESI, Nebraska, Omaha). The system is not only inert (all-flouropolymer flow paths), but is also very flexible and can easily facilitate different resins, samples, and reagent types. When programmed, precise and accurate user defined volumes and flow rates are implemented to automatically load samples, wash the column, condition the column and elute fractions. Unattended, the automated, low-pressure ion exchange chromatography system can process up to 60 samples overnight. Excellent reproducibility, reliability, recovery, with low blank and carry over for samples in a variety of different matrices, have been demonstrated to give accurate and precise isotopic ratios within analytical error for several isotopic systems (B, Ca, Fe, Cu, Zn, Sr, Cd, Pb and U). This illustrates the potential of the new prepFAST-MC™ (ESI, Nebraska, Omaha) as a powerful tool in radiogenic and non-traditional isotope research.

Mechanical properties and rapid low-temperature consolidation of nanocrystalline Cu-ZrO2 composites by pulsed current activated heating

NASA Astrophysics Data System (ADS)

Kang, Bo-Ram; Yoon, Jin-kook; Hong, Kyung-Tae; Shon, In-Jin

2015-07-01

Metal-ceramic compositr can be obtained with an optimum combination of low density, high oxidation resistance, and high hardness of the ceramic and toughness of the metal. Therefore, metal matrix composites are recognized as candidates for aerospace, automotive, biomaterials, and defense applications. Despite its many attractive properties, the low fracture toughness of ZrO2 limits its wide application. One of the most obvious tactics to improve the mechanical properties has been to fabricate a nanostructured material and composite material. Nano-powders of Cu and ZrO2 were synthesized from 2CuO and Zr powders by high-energy ball milling. Nanocrystalline 2Cu-ZrO2 composite was consolidated within 5 minutes from mechanically synthesized powders of ZrO2 and 2Cu at low temperature, by a pulsed current activated sintering method. The relative density of the composite was 98.5%. The fracture toughness of 2Cu-ZrO2 composite in this study is higher than that of monolithic ZrO2, without great decrease of hardness.

Preparation of CuO/NiO composite nanofibers by electrospinning and their application for electro-catalytic oxidation of hydrazine

NASA Astrophysics Data System (ADS)

Hosseini, Sayed Reza; Ghasemi, Shahram; Kamali-Rousta, Mina

2017-03-01

In present work, polyvinyl alcohol/copper acetate-nickel acetate composite nanofibers (PVA/Cu(OAc)2-Ni(OAc)2 NFs) with various weight percentages of Cu(OAc)2:Ni(OAc)2 such as 25:75, 50:50 and 75:25 are fabricated by electrospinning method. After this, the CuO/NiO composite NFs are produced after thermal treatment. A calcination temperature at about 600 °C is determined by thermal gravimetric analysis. Field-emission scanning electron microscopy (FE-SEM) for morphology characterization indicates that large quantities of the prepared PVA/Cu(OAc)2-Ni(OAc)2 composite fibers have smooth and bead-free surfaces. Fourier transform infrared spectroscopy, FE-SEM and energy dispersive X-ray spectroscopy are used to characterize the CuO/NiO composites. According to FE-SEM results, with increasing of Cu(OAc)2 content in polymeric solution, the fibers don't remain as continuous structures after calcination and accumulate in the form of nanoparticles. Also, a carbon paste electrode (CPE) bulky modified with CuO/NiO composites is used for investigation of the electro-catalytic oxidation of hydrazine hydrate in NaOH solution. The catalytic activities of the synthesized catalysts are studied through cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. The obtained results demonstrate that the most appropriate proportion of Cu(OAc)2:Ni(OAc)2 in electrospinning solution to enhance the electro-catalytic ability is 25:75.

Effect of milling time on microstructure and mechanical properties of Cu-Ni-graphite composites

NASA Astrophysics Data System (ADS)

Wang, Yiran; Gao, Yimin; Li, Yefei; Zhang, Chao; Huang, Xiaoyu; Zhai, Wenyan

2017-09-01

Cu-Ni-graphite composites are intended for application in switch slide baseplate materials. The microstructure of the composites depends strongly on the ball milling time, and a suitable time can significantly improve the properties of the Cu-Ni-graphite composites. In this study, a two-step milling method was employed. The morphology evolution and microstructural features of the powder was characterized at different milling times. Afterwards, the Cu-Ni-graphite composites were prepared in the process of cold pressing, sintering, re-pressing and re-sintering as a function of the different milling times. Finally, both the microstructure and mechanical properties of the Cu-Ni-graphite composites are discussed. The results show that no new phase was generated during the milling process. The morphology evolution of the mixture of Cu/Ni powder changed from spherical-like to cubic-like, plate-like and flake-like with an increasing milling time. The microstructure of the composites consisted of α-phase and graphite. The boundary area and quantity of pores changed as the milling time increased. The relative density, hardness and flexural strength reached maximum values at 15 h of milling time.

Copper-Hydroperoxo Mediated N-Debenzylation Chemistry Mimicking Aspects of Copper Monoxygenases

PubMed Central

Maiti, Debabrata; Narducci Sarjeant, Amy A.; Karlin, Kenneth D.

2008-01-01

Substantial oxidative N-debenzylation reaction along with PhCH=O formation occurs from a hydroperoxo copper(II) complex which has a dibenzylamino substrate (-N(CH2Ph)2 appended as a substituent on one pyridyl group of its tripodal tetradentate TMPA {≡ TPA ≡ tris(2-pyridylmethyl)amine)} ligand framework. During the course of the (LN(CH2Ph)2)CuII(−OOH) reactivity, formation of a substrate and −OOH (an oxygen atom) derived alkoxo CuII(−OR) complex occurs. The observation that the same CuII(−OR) species occurs from CuI/PhIO chemistry suggests the possibility that a copper-oxo (cupryl) reactive intermediate forms during alkoxo species formation, and new ESI-MS data obtained provides some further support for this high-valent intermediate. Net H-atom abstraction chemistry is proposed, based on kinetic isotope effect studies provided here and that previously published for a closely related CuII(−OOH) species incorporating dimethylamine (-N(CH3)2) as the internal substrate (J. Am. Chem. Soc. 2007, 129, 6720-6721); the CuI/PhIO reactivity, with similar isotope effect results, provides further support. The reactivity of these chemical systems closely resembles proposed oxidative N-dealkylation mechanisms effected by the copper-monooxygenases dopamine β-monooxygenase (DβM) or peptidylglycine-α-hydroxylating monooxygenase (PHM). PMID:18783212

Petrographic, fluid inclusion and isotopic study of the Dikulushi Cu-Ag deposit, Katanga (D.R.C.): implications for exploration

NASA Astrophysics Data System (ADS)

Haest, Maarten; Muchez, Philippe; Dewaele, Stijn; Boyce, Adrian J.; von Quadt, Albrecht; Schneider, Jens

2009-07-01

The Dikulushi Cu-Ag vein-type deposit is located on the Kundelungu Plateau, in the southeastern part of the Democratic Republic of Congo (D.R.C.). The Kundelungu Plateau is situated to the north of the Lufilian Arc that hosts the world-class stratiform Cu-Co deposits of the Central African Copperbelt. A combined petrographic, fluid inclusion and stable isotope study revealed that the mineralisation at Dikulushi developed during two spatially and temporally distinct mineralising episodes. An early Cu-Pb-Zn-Fe mineralisation took place during the Lufilian Orogeny in a zone of crosscutting EW- and NE-oriented faults and consists of a sequence of sulphides that precipitated from moderate-temperature, saline H2O-NaCl-CaCl2-rich fluids. These fluids interacted extensively with the country rocks. Sulphur was probably derived from thermochemical reduction of Neoproterozoic seawater sulphate. Undeformed, post-orogenic Cu-Ag mineralisation remobilised the upper part of the Cu-Pb-Zn-Fe mineralisation in an oxidising environment along reactivated and newly formed NE-oriented faults in the eastern part of the deposit. This mineralisation is dominated by massive Ag-rich chalcocite that precipitated from low-temperature H2O-NaCl-KCl fluids, generated by mixing of moderate- and low-saline fluids. The same evolution in mineralisation assemblages and types of mineralising fluids is observed in three other Cu deposits on the Kundelungu Plateau. Therefore, the recognition of two distinct types of (vein-type) mineralisation in the study area has a profound impact on the exploration in the Kundelungu Plateau region. The identification of a Cu-Ag type mineralisation at the surface could imply the presence of a Cu-Pb-Zn-Fe mineralisation at depth.

Porphyry Cu-Au mineralization in the Mirkuh Ali Mirza magmatic complex, NW Iran

NASA Astrophysics Data System (ADS)

Maghsoudi, A.; Yazdi, M.; Mehrpartou, M.; Vosoughi, M.; Younesi, S.

2014-01-01

The Mirkuh Ali Mirza Cu-Au porphyry system in East Azerbaijan Province is located on the western part of the Cenozoic Alborz-Azerbaijan volcanic belt. The belt is also an important Cu-Mo-Au metallogenic province in northwestern Iran. The exposed rocks in the study area consist of a volcaniclastic sequence, subvolcanic rocks and intermediate to mafic lava flows of Neogene age. The volcanic rocks show a typical subduction-related magmatic arc geological and geochemical signature, with low concentration of Nb, Ta, and Ti. Mineralization is hosted by Neogene dacitic tuff and porphyritic dacite situated at the intersections of northeast and northwest faults. Field observations, alteration zonation, geochemical haloes and isotopic data of the Mirkuh Ali Mirza magmatic complex show similarities with typical convergent margin Cu-Au porphyry type deposits. The following features confirm the classic model for Cu-Au porphyry systems: (a) close spatial association with high-K calcalkaline to shoshonitic rock related to post-collision extensional setting (b) low grade Cu (0.57%) (c) stockworks as well as disseminated sulfides (c) zonality of the alteration patterns from intense phyllic at the center to outward weak-phyllic, argillic, and propylitic (d) the presence of a pyritic halo (e) accompanied by sheeted veins and low-sulfidation epithermal gold (f) mineralization spatially associated with intersection of structures, (g) genetically related to diorite porphyry stocks at depth (h) geochemical zonation of (Cu ± Au ± Ag ± Bi) → (Cu + Mo ± Bi ± Au ± Pb ± Zn ± As) → (Au + Mo ± Pb ± Zn) → (As + Ag + Sb + Mn + Ba + Pb + Zn + Hg) → Hg from center to outwards (i) The range of sulfur isotopic values is approximately zero (interpreted to have magmatic source) and similar to other subduction-related porphyry Cu deposits.

Fabrication and photocatalytic property of magnetic NiFe2O4/Cu2O composites

NASA Astrophysics Data System (ADS)

He, Zuming; Xia, Yongmei; Tang, Bin; Su, Jiangbin

2017-09-01

Magnetically separable NiFe2O4/Cu2O composites were successfully synthesized by a two-step method. The samples were characterized by XRD, XPS, SEM and VSM as well as their PL spectra and UV-vis adsorption spectra. The results showed that the NiFe2O4/Cu2O composites were composed of cubic-structured Cu2O and spinel-structured NiFe2O4, were able to absorb a large amount of visible light, exhibited excellent photocatalytic activity under simulated solar light irradiation and could be easily separated by an external magnetic field. The NiFe2O4/Cu2O composites exhibited higher photocatalytic performance than that of a single semiconductor. It was found that the prominently enhanced photocatalytic performance of NiFe2O4/Cu2O composites was ascribed to the effective separation of photo-generated electron-hole pairs and the effective generation of the hydroxyl radical •OH.

Statistical clumped isotope signatures

PubMed Central

Röckmann, T.; Popa, M. E.; Krol, M. C.; Hofmann, M. E. G.

2016-01-01

High precision measurements of molecules containing more than one heavy isotope may provide novel constraints on element cycles in nature. These so-called clumped isotope signatures are reported relative to the random (stochastic) distribution of heavy isotopes over all available isotopocules of a molecule, which is the conventional reference. When multiple indistinguishable atoms of the same element are present in a molecule, this reference is calculated from the bulk (≈average) isotopic composition of the involved atoms. We show here that this referencing convention leads to apparent negative clumped isotope anomalies (anti-clumping) when the indistinguishable atoms originate from isotopically different populations. Such statistical clumped isotope anomalies must occur in any system where two or more indistinguishable atoms of the same element, but with different isotopic composition, combine in a molecule. The size of the anti-clumping signal is closely related to the difference of the initial isotope ratios of the indistinguishable atoms that have combined. Therefore, a measured statistical clumped isotope anomaly, relative to an expected (e.g. thermodynamical) clumped isotope composition, may allow assessment of the heterogeneity of the isotopic pools of atoms that are the substrate for formation of molecules. PMID:27535168

Photoelectrochemical Properties of CuS-GeO2-TiO2 Composite Coating Electrode

PubMed Central

Wen, Xinyu; Zhang, Huawei

2016-01-01

The ITO (indium tin oxide) conductive glass-matrix CuS-GeO2-TiO2 composite coating was generated via EPD (electrophoretic deposition) and followed by a sintering treatment at 450°C for 40 minutes. Characterizations of the CuS-GeO2-TiO2 composite coating were taken by SEM (scanning electron microscope), XRD (X-ray diffraction), EDX (energy dispersive X-ray), UV-Vis DRS (ultraviolet-visible diffuse reflection spectrum), and FT-IR (Fourier transform infrared spectroscopy). Results showed that CuS and GeO2 had dispersed in this CuS-GeO2-TiO2 composite coating (mass percentages for CuS and GeO2 were 1.23% and 2.79%, respectively). The electrochemical studies (cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and Tafel polarization) of this CuS-GeO2-TiO2 composite coating electrode were performed in pH = 9.51 Na2CO3-NaHCO3 buffer solution containing 0.50 mol/L CH3OH under the conditions of visible light, ultraviolet light (λ = 365 nm), and dark (without light irradiation as control), respectively. Electrochemical studies indicated that this CuS-GeO2-TiO2 composite coating electrode had better photoelectrocatalytic activity than the pure TiO2 electrode in the electrocatalysis of methanol under visible light. PMID:27055277

Photoelectrochemical Properties of CuS-GeO2-TiO2 Composite Coating Electrode.

PubMed

Wen, Xinyu; Zhang, Huawei

2016-01-01

The ITO (indium tin oxide) conductive glass-matrix CuS-GeO2-TiO2 composite coating was generated via EPD (electrophoretic deposition) and followed by a sintering treatment at 450°C for 40 minutes. Characterizations of the CuS-GeO2-TiO2 composite coating were taken by SEM (scanning electron microscope), XRD (X-ray diffraction), EDX (energy dispersive X-ray), UV-Vis DRS (ultraviolet-visible diffuse reflection spectrum), and FT-IR (Fourier transform infrared spectroscopy). Results showed that CuS and GeO2 had dispersed in this CuS-GeO2-TiO2 composite coating (mass percentages for CuS and GeO2 were 1.23% and 2.79%, respectively). The electrochemical studies (cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and Tafel polarization) of this CuS-GeO2-TiO2 composite coating electrode were performed in pH = 9.51 Na2CO3-NaHCO3 buffer solution containing 0.50 mol/L CH3OH under the conditions of visible light, ultraviolet light (λ = 365 nm), and dark (without light irradiation as control), respectively. Electrochemical studies indicated that this CuS-GeO2-TiO2 composite coating electrode had better photoelectrocatalytic activity than the pure TiO2 electrode in the electrocatalysis of methanol under visible light.

The effect of rotating magnetic field on the microstructure of in situ TiB2/Cu composites

NASA Astrophysics Data System (ADS)

Zou, C.; Kang, H.; Li, R.; Li, M.; Wang, W.; Chen, Z.; Wang, T.

2016-03-01

Nano ceramic particulate reinforced metal matrix composites are confronted with the problem of particle aggregation emerging in the process of solidification. It sharply deteriorates the mechanical properties of the composites. In order to improve the microstructure and particle distribution, in situ TiB2/Cu composites were prepared using Ti and Cu-B master alloys in a vacuum medium frequency induction furnace equipped with a rotating magnetic field (RMF). The effect of RMF magnetic field intensity employed on the microstructure and particles distribution of the TiB2/Cu composites were investigated. The results show that with the applied RMF, TiB2 particles are homogeneously distributed in the copper matrix, which significantly improves the mechanical properties of TiB2/Cu composites. The mechanism of RMF may be ascribed to the following two aspects. On the one hand, the electromagnetic body force generated by appropriate RMF drives forced convection in the equatorial plane of composite melt during solidification. On the other hand, a secondary flow in the meridional plane is engendered by a radial pressure gradient, thus making a strong agitation in the melt. These two effects result in a homogenous dispersion of TiB2 particles in the copper matrix, and hence excellent properties of TiB2/Cu composites were obtained.

Spatial patterns of throughfall isotopic composition at the event and seasonal timescales

Treesearch

Scott T. Allen; Richard F. Keim; Jeffrey J. McDonnell

2015-01-01

Spatial variability of throughfall isotopic composition in forests is indicative of complex processes occurring in the canopy and remains insufficiently understood to properly characterize precipitation inputs to the catchment water balance. Here we investigate variability of throughfall isotopic composition with the objectives: (1) to quantify the spatial variability...

The Effects of Core Composition on Iron Isotope Fractionation During Planetary Differentiation

NASA Astrophysics Data System (ADS)

Elardo, S. M.; Shahar, A.; Caracas, R.; Mock, T. D.; Sio, C. K. I.

2018-05-01

High pressure and temperature isotope exchange experiments and density functional theory calculations show how the composition of planetary cores affects the fractionation of iron isotopes during planetary differentiation.

Weathering and vegetation controls on nickel isotope fractionation in surface ultramafic environments (Albania)

NASA Astrophysics Data System (ADS)

Estrade, Nicolas; Cloquet, Christophe; Echevarria, Guillaume; Sterckeman, Thibault; Deng, Tenghaobo; Tang, YeTao; Morel, Jean-Louis

2015-08-01

The dissolved nickel (Ni) isotopic composition of rivers and oceans presents an apparent paradox. Even though rivers represent a major source of Ni in the oceans, seawater is more enriched in the heavier isotopes than river-water. Additional sources or processes must therefore be invoked to account for the isotopic budget of dissolved Ni in seawater. Weathering of continental rocks is thought to play a major role in determining the magnitude and sign of isotopic fractionation of metals between a rock and the dissolved product. We present a study of Ni isotopes in the rock-soil-plant systems of several ultramafic environments. The results reveal key insights into the magnitude and the control of isotopic fractionation during the weathering of continental ultramafic rocks. This study introduces new constraints on the influence of vegetation during the weathering process, which should be taken into account in interpretations of the variability of Ni isotopes in rivers. The study area is located in a temperate climate zone within the ophiolitic belt area of Albania. The serpentinized peridotites sampled present a narrow range of heavy Ni isotopic compositions (δ60Ni = 0.25 ± 0.16 ‰, 2SD n = 2). At two locations, horizons within two soil profiles affected by different degrees of weathering all presented light isotopic compositions compared to the parent rock (Δ60Nisoil-rock up to - 0.63 ‰). This suggests that the soil pool takes up the light isotopes, while the heavier isotopes remain in the dissolved phase. By combining elemental and mineralogical analyses with the isotope compositions determined for the soils, the extent of fractionation was found to be controlled by the secondary minerals formed in the soil. The types of vegetation growing on ultramafic-derived soils are highly adapted and include both Ni-hyperaccumulating species, which can accumulate several percent per weight of Ni, and non-accumulating species. Whole-plant isotopic compositions were found to be isotopically heavier than the soil (Δ60Niwhole plant-soil up to 0.40‰). Fractions of Ni extracted by DTPA (diethylenetriaminepentaacetic acid) presented isotopically heavy compositions compared to the soil (Δ60NiDTPA-soil up to 0.89‰), supporting the hypothesis that the dissolved Ni fraction controlled by weathering has a heavy isotope signature. The non-hyperaccumulators (n = 2) were inclined to take up and translocate light Ni isotopes with a large degree of fractionation (Δ60Nileaves-roots up to - 0.60 ‰). For Ni-hyperaccumulators (n = 7), significant isotopic fractionation was observed in the plants in their early growth stages, while no fractionation occurred during later growth stages, when plants are fully loaded with Ni. This suggests that (i) the high-efficiency translocation process involved in hyperaccumulators does not fractionate Ni isotopes, and (ii) the root uptake process mainly controls the isotopic composition of the plant. In ultramafic contexts, vegetation composed of hyperaccumulators can significantly influence isotopic compositions through its remobilization in the upper soil horizon, thereby influencing the isotopic balance of Ni exported to rivers.

Influences on the stable oxygen and carbon isotopes in gerbillid rodent teeth in semi-arid and arid environments: Implications for past climate and environmental reconstruction

NASA Astrophysics Data System (ADS)

Jeffrey, Amy; Denys, Christiane; Stoetzel, Emmanuelle; Lee-Thorp, Julia A.

2015-10-01

The stable isotope composition of small mammal tissues has the potential to provide detailed information about terrestrial palaeoclimate and environments, because their remains are abundant in palaeontological and archaeological sites, and they have restricted home ranges. Applications to the Quaternary record, however, have been sparse and limited by an acute lack of understanding of small mammal isotope ecology, particularly in arid and semi-arid environments. Here we document the oxygen and carbon isotope composition of Gerbillinae (gerbil) tooth apatite across a rainfall gradient in northwestern Africa, in order to test the relative influences of the 18O/16O in precipitation or moisture availability on gerbil teeth values, the sensitivity of tooth apatite 13C/12C to plant responses to moisture availability, and the influence of developmental period on the isotopic composition of gerbil molars and incisors. The results show that the isotopic composition of molars and incisors from the same individuals differs consistent with the different temporal periods reflected by the teeth; molar teeth are permanently rooted and form around the time of birth, whereas incisors grow continuously. The results indicate that tooth choice is an important consideration for applications as proxy Quaternary records, but also highlights a new potential means to distinguish seasonal contexts. The oxygen isotope composition of gerbil tooth apatite is strongly correlated with mean annual precipitation (MAP) below 600 mm, but above 600 mm the teeth reflect the oxygen isotope composition of local meteoric water instead. Predictably, the carbon isotope composition of the gerbil teeth reflected C3 and C4 dietary inputs, however arid and mesic sites could not be distinguished because of the high variability displayed in the carbon isotope composition of the teeth due to the microhabitat and short temporal period reflected by the gerbil. We show that the oxygen isotope composition of small mammal teeth strongly reflects moisture availability in semi-arid and arid environments and would provide an excellent record of palaeo-aridity in a terrestrial setting. The results illustrate that an understanding of an animal's physiology is essential for interpreting the animal's isotopic responses to external contexts, especially in arid zones.

Stable lead isotopic analyses of historic and contemporary lead contamination of San Francisco Bay estuary

USGS Publications Warehouse

Ritson, P.I.; Bouse, R.M.; Flegal, A.R.; Luoma, S.N.

1999-01-01

Variations in stable lead isotopic composition (240Pb, 206Pb, 207Pb, 208Pb) in three sediment cores from the San Francisco Bay estuary document temporal changes in sources of lead during the past two centuries. Sediment, with lead from natural geologic sources, and relatively homogeneous lead isotopic compositions are overlain by sediments whose isotopic compositions indicate change in the sources of lead associated with anthropogenic modification of the estuary. The first perturbations of lead isotopic composition in the cores occur in the late 1800s concordant with the beginning of industrialization around the estuary. Large isotopic shifts, toward lower 206Pb/207Pb, occur after the turn of the century in both Richardson and San Pablo Bays. A similar relationship among lead isotopic compositions and lead concentrations in both Bays suggest contamination from the same source (a lead smelter). The uppermost sediments (post 1980) of all cores also have a relatively homogenous lead isotopic composition distinct from pre-anthropogenic and recent aerosol signatures. Lead isotopic compositions of leachates from fourteen surface sediments and five marsh samples from the estuary were also analyzed. These analyses suggest that the lead isotopic signature identified in the upper horizons of the cores is spatially homogeneous among recently deposited sediments throughout the estuary. Current aerosol lead isotopic compositions [Smith, D.R., Niemeyer, S., Flegal, A.R., 1992. Lead sources to California sea otters: industrial inputs circumvent natural lead biodepletion mechanisms. Environmental Research 57, 163-175] are distinct from the isotopic compositions of the surface sediments, suggesting that the major source of lead is cycling of historically contaminated sediments back through the water column. Both the upper core sediments and surface sediments apparently derive their lead predominantly from sources internal to the estuary. These results support the idea that geochemical cycling of lead between sediments and water accounts for persistently elevated lead concentrations in the water column despite 10-fold reduction of external source inputs to San Francisco Bay [Flegal, A.R., Rivera-Duarte, I., Ritson, P.I., Scelfo, G., Smith, G.J., Gordon, M., Sanudo-Wilhelmy, S.A., 1996. Metal contamination in San Francisco Waters: historic perturbations, contemporary concentrations, and future considerations in San Francisco Bay. In: Hollobaugh, J.T. (Ed.), The Ecosystem. AAAS, pp. 173-188].

Preparation of tungsten fiber reinforced-tungsten/copper composite for plasma facing component

NASA Astrophysics Data System (ADS)

He, Gang; Xu, Kunyuan; Guo, Shibin; Qian, Xueqiang; Yang, Zengchao; Liu, Guanghua; Li, Jiangtao

2014-12-01

W fiber reinforced-W/Cu composite is designed as a transition layer between CuCrZr heat sink material and W plasma facing material. A novel method was developed for the preparation of W fiber reinforced-W/Cu composite by combining combustion synthesis with centrifugal infiltration. Cu melt with a transient temperature over 2000 °C produced by the thermite reaction was infiltrated into the W powder and fiber bed with the assistance of a high gravity field. It was found that the W particles were sintered and bonded to the W fibers due to the high temperature produced by the thermite reaction. The bending strength of W/Cu composite improved 12.7% through W fibers reinforcement.

Hot Deformation Behavior and Processing Maps of Diamond/Cu Composites

NASA Astrophysics Data System (ADS)

Zhang, Hongdi; Liu, Yue; Zhang, Fan; Zhang, Di; Zhu, Hanxing; Fan, Tongxiang

2018-03-01

The hot deformation behaviors of 50 vol pct uncoated and Cr-coated diamond/Cu composites were investigated using hot isothermal compression tests under the temperature and strain rate ranging from 1073 K to 1273 K (800 °C to 1000 °C) and from 0.001 to 5 s-1, respectively. Dynamic recrystallization was determined to be the primary restoration mechanism during deformation. The Cr3C2 coating enhanced the interfacial bonding and resulted in a larger flow stress for the Cr-coated diamond/Cu composites. Moreover, the enhanced interfacial affinity led to a higher activation energy for the Cr-coated diamond/Cu composites (238 kJ/mol) than for their uncoated counterparts (205 kJ/mol). The strain-rate-dependent constitutive equations of the diamond/Cu composites were derived based on the Arrhenius model, and a high correlation (R = 0.99) was observed between the calculated flow stresses and experimental data. With the help of processing maps, hot extrusions were realized at 1123 K/0.01 s-1 and 1153 K/0.01 s-1 (850 °C/0.01 s-1 and 880 °C/0.01 s-1) for the uncoated and coated diamond/Cu composites, respectively. The combination of interface optimization and hot extrusion led to increases of the density and thermal conductivity, thereby providing a promising route for the fabrication of diamond/Cu composites.

Hot Deformation Behavior and Processing Maps of Diamond/Cu Composites

NASA Astrophysics Data System (ADS)

Zhang, Hongdi; Liu, Yue; Zhang, Fan; Zhang, Di; Zhu, Hanxing; Fan, Tongxiang

2018-06-01

The hot deformation behaviors of 50 vol pct uncoated and Cr-coated diamond/Cu composites were investigated using hot isothermal compression tests under the temperature and strain rate ranging from 1073 K to 1273 K (800 °C to 1000 °C) and from 0.001 to 5 s-1, respectively. Dynamic recrystallization was determined to be the primary restoration mechanism during deformation. The Cr3C2 coating enhanced the interfacial bonding and resulted in a larger flow stress for the Cr-coated diamond/Cu composites. Moreover, the enhanced interfacial affinity led to a higher activation energy for the Cr-coated diamond/Cu composites (238 kJ/mol) than for their uncoated counterparts (205 kJ/mol). The strain-rate-dependent constitutive equations of the diamond/Cu composites were derived based on the Arrhenius model, and a high correlation ( R = 0.99) was observed between the calculated flow stresses and experimental data. With the help of processing maps, hot extrusions were realized at 1123 K/0.01 s-1 and 1153 K/0.01 s-1 (850 °C/0.01 s-1 and 880 °C/0.01 s-1) for the uncoated and coated diamond/Cu composites, respectively. The combination of interface optimization and hot extrusion led to increases of the density and thermal conductivity, thereby providing a promising route for the fabrication of diamond/Cu composites.

Isotopic compositions of the elements, 2001

USGS Publications Warehouse

Böhlke, J.K.; De Laeter, J. R.; De Bievre, P.; Hidaka, H.; Peiser, H.S.; Rosman, K.J.R.; Taylor, P.D.P.

2005-01-01

The Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry completed its last review of the isotopic compositions of the elements as determined by isotope-ratio mass spectrometry in 2001. That review involved a critical evaluation of the published literature, element by element, and forms the basis of the table of the isotopic compositions of the elements (TICE) presented here. For each element, TICE includes evaluated data from the “best measurement” of the isotope abundances in a single sample, along with a set of representative isotope abundances and uncertainties that accommodate known variations in normal terrestrial materials. The representative isotope abundances and uncertainties generally are consistent with the standard atomic weight of the element Ar(E)">Ar(E)Ar(E) and its uncertainty U[Ar(E)]">U[Ar(E)]U[Ar(E)] recommended by CAWIA in 2001.

Calcium Isotopic Compositions of Forearc Sediments from DSDP Site 144

NASA Astrophysics Data System (ADS)

Zhang, Z.; Zhu, H.; Nan, X.; Li, X.; Huang, F.

2016-12-01

It is important to investigate calcium isotopic compositions of reservoirs of the Earth for better application of Ca isotopes into studies of a variety of geochemical problems. Because Ca isotopic compositions for igneous rocks and carbonates are increasingly reported, this maybe bring new requirements on carefully understanding the isotopic compositions of subducted marine sediments. Marine sediments mainly contains carbonates and clays, controlling the compositions of slab-derived materials which are added to the mantle wedge. Obviously, it could have different elemental and calcium isotopic compositions with marine carbonate. Thus, it could also put biases on calcium isotopic signatures of basalts resulted from recycling oceanic carbonate into the mantle. Here, we report calcium isotopic compositions of 17 sediment samples from Deep Sea Drilling Project (DSDP) site 144 (09°27.23' N, 54°20.52' W) which is located about 400 km north of Surinam on the northern flank of the Demerara Rise with a water depth of 2957 meters. These samples have CaO contents ranging from 14.56 wt.% to 41.46 wt.% with an average of 29.61 ± 18.21 (2SD), δ44/40Ca ranges from 0.19 to 0.58 (relative to SRM915a) with an average of 0.40 ± 0.22 (2SD). These carbonate-rich sediments can be used to represent an endmember with high CaO content and low δ44/40Ca, which could modify chemical composition of the upper mantle and subduction zone lavas if they are recycled to the convective mantle during subduction. The positive linear correlation between CaO and δ44/40Ca in the sediments cannot be explained by a simple mixing between marine carbonate and clay. Instead, δ44/40Ca of these samples roughly increase from the Upper Cretaceous to the Early Oligocene, which might reflect the evolution of calcium isotopic compositions of seawater through time.

Theoretical Investigation of Calculating Temperatures in the Combining Zone of Cu/Fe Composite Plate Jointed by Explosive Welding

NASA Astrophysics Data System (ADS)

Qu, Y. D.; Zhang, W. J.; Kong, X. Q.; Zhao, X.

2016-03-01

The heat-transfer behavior of the interface of Flyer plate (or Base Plate) has great influence on the microcosmic structures, stress distributions, and interface distortion of the welded interface of composite plates by explosive welding. In this paper, the temperature distributions in the combing zone are studied for the case of Cu/Fe composite plate jointed by explosive welding near the lower limit of explosive welding. The results show that Flyer plate (Cu plate) and Base Plate (Fe plate) firstly almost have the same melting rate in the explosive welding process. Then, the melting rate of Cu plate becomes higher than that of Fe plate. Finally, the melt thicknesses of Cu plate and Fe plate trend to be different constants, respectively. Meanwhile, the melting layer of Cu plate is thicker than that of Fe plate. The research could supply some theoretical foundations for calculating the temperature distribution and optimizing the explosive welding parameters of Cu/Fe composite plate to some extent.

Graphite fiber/copper composites prepared by spontaneous infiltration

NASA Astrophysics Data System (ADS)

Wang, Hongbao; Tao, Zechao; Li, Xiangfen; Yan, Xi; Liu, Zhanjun; Guo, Quangui

2018-05-01

The major bottleneck in developing graphite fiber reinforced copper (GF/Cu) composites is the poor wettability of Cu/graphite system. Alloying element of chromium (Cr) is introduced to improve the wettability of liquid copper on graphite. Sessile drop method experiments illustrate that the contact angle of liquid Cu-Cr (1.0 wt.%) alloy on graphite substrate decreases to 43° at 1300 °C. The improvement of wettability is related to the formation of chromium carbide layer at interface zone. Based on the wetting experiment, a spontaneous infiltration method for preparing GF/Cu composites is proposed. Unidirectional GF preforms are infiltrated by Cu-Cr alloys without external pressure in a tubular furnace. Results reveal that the GF preform can be fully infiltrated by Cu-Cr alloy (8 wt.%) spontaneously when fiber volume fraction is 40%. The coefficient of thermal expansion (CTE) of GF/Cu-Cr (8.0 wt.%) composites is 4.68 × 10-6/K along the longitudinal direction.

Microstructure and properties of Cu-Sn-Zn-TiO 2 nano-composite coatings on mild steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Weidong; Cao, Di; Jin, Yunxue

Cu-Sn-Zn coatings have been widely used in industry for their unique properties, such as good conductivity, high corrosion resistance and excellent solderability. To further improve the mechanical performance of Cu-Sn-Zn coatings, powder-enhanced method was applied and Cu-Sn-Zn-TiO 2 nano-composite coatings with different TiO 2 concentration were fabricated. The microstructure of Cu-Sn-Zn-TiO 2 nano-composite coatings were investigated by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). The mechanical properties of coatings including microhardness and wear resistance were studied. The results indicate that the incorporation of TiO 2 nanoparticle can significantly influence the properties of Cu-Sn-Zn coatings. The microhardness of Cu-Sn-Zn coatingmore » was increased to 383 HV from 330 HV with 1 g/L TiO 2 addition. Also, the corrosion resistance of coating was enhanced. The effects of TiO 2 nanoparticle concentration on the microstructure, mechanical properties and corrosion resistance of Cu-Sn-Zn-TiO 2 nano-composite coatings were discussed.« less

Microstructure and properties of Cu-Sn-Zn-TiO 2 nano-composite coatings on mild steel

DOE PAGES

Gao, Weidong; Cao, Di; Jin, Yunxue; ...

2018-04-18

Cu-Sn-Zn coatings have been widely used in industry for their unique properties, such as good conductivity, high corrosion resistance and excellent solderability. To further improve the mechanical performance of Cu-Sn-Zn coatings, powder-enhanced method was applied and Cu-Sn-Zn-TiO 2 nano-composite coatings with different TiO 2 concentration were fabricated. The microstructure of Cu-Sn-Zn-TiO 2 nano-composite coatings were investigated by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). The mechanical properties of coatings including microhardness and wear resistance were studied. The results indicate that the incorporation of TiO 2 nanoparticle can significantly influence the properties of Cu-Sn-Zn coatings. The microhardness of Cu-Sn-Zn coatingmore » was increased to 383 HV from 330 HV with 1 g/L TiO 2 addition. Also, the corrosion resistance of coating was enhanced. The effects of TiO 2 nanoparticle concentration on the microstructure, mechanical properties and corrosion resistance of Cu-Sn-Zn-TiO 2 nano-composite coatings were discussed.« less

Cu2O/CuO Bilayered Composite as a High-Efficiency Photocathode for Photoelectrochemical Hydrogen Evolution Reaction

PubMed Central

Yang, Yang; Xu, Di; Wu, Qingyong; Diao, Peng

2016-01-01

Solar powered hydrogen evolution reaction (HER) is one of the key reactions in solar-to-chemical energy conversion. It is desirable to develop photocathodic materials that exhibit high activity toward photoelectrochemical (PEC) HER at more positive potentials because a higher potential means a lower overpotential for HER. In this work, the Cu2O/CuO bilayered composites were prepared by a facile method that involved an electrodeposition and a subsequent thermal oxidation. The resulting Cu2O/CuO bilayered composites exhibited a surprisingly high activity and good stability toward PEC HER, expecially at high potentials in alkaline solution. The photocurrent density for HER was 3.15 mA·cm−2 at the potential of 0.40 V vs. RHE, which was one of the two highest reported at the same potential on copper-oxide-based photocathode. The high photoactivity of the bilayered composite was ascribed to the following three advantages of the Cu2O/CuO heterojunction: (1) the broadened light absorption band that made more efficient use of solar energy, (2) the large space-charge-region potential that enabled a high efficiency for electron-hole separation, and (3) the high majority carrier density that ensured a faster charge transportation rate. This work reveals the potential of the Cu2O/CuO bilayered composite as a promising photocathodic material for solar water splitting. PMID:27748380

Observation of new neutron-rich Mn, Fe, Co, Ni, and Cu isotopes in the vicinity of 78Ni

NASA Astrophysics Data System (ADS)

Sumikama, T.; Nishimura, S.; Baba, H.; Browne, F.; Doornenbal, P.; Fukuda, N.; Franchoo, S.; Gey, G.; Inabe, N.; Isobe, T.; John, P. R.; Jung, H. S.; Kameda, D.; Kubo, T.; Li, Z.; Lorusso, G.; Matea, I.; Matsui, K.; Morfouace, P.; Mengoni, D.; Napoli, D. R.; Niikura, M.; Nishibata, H.; Odahara, A.; Sahin, E.; Sakurai, H.; Söderström, P.-A.; Stefan, G. I.; Suzuki, D.; Suzuki, H.; Takeda, H.; Taniuchi, R.; Taprogge, J.; Vajta, Zs.; Watanabe, H.; Werner, V.; Wu, J.; Xu, Z. Y.; Yagi, A.; Yoshinaga, K.

2017-05-01

Neutron-rich nuclei in the vicinity of 78Ni were produced using a 238U beam at the RIKEN Radioactive Isotope Beam Factory. The particle-identification plot for the in-flight fission fragments highlights the first observation of eight new isotopes: 73Mn, 76Fe, Co,7877, 80,81,82Ni, and 83Cu. Although the β -decay half-lives of 77Co and 80Ni were recently reported by Xu et al. [Phys. Rev. Lett. 113, 032505 (2014)], 10.1103/PhysRevLett.113.032505 using data from the same experiment, the current work provides the first direct, quantitative evidence for the existence of these isotopes. The experimental production cross sections are reproduced in a satisfactory manner by theoretical predictions. An odd-even staggering of the cross sections was observed, and the effect appears to become more pronounced for the most exotic nuclei that were investigated. The staggering effect was interpreted as an increase of the neutron-evaporation probability for odd-N isotopes, owing to the decrease of the neutron-separation energy, Sn. The predicted cross section for 80Ni is significantly overestimated, which may be related to a weak binding of the neutron pair above the N =50 shell closure.

The Effect of Film Composition on the Texture and Grain Size of CuInS2 Prepared by Spray Pyrolysis

NASA Technical Reports Server (NTRS)

Jin, Michael H.; Banger, Kulinder K.; Harris, Jerry D.; Hepp, Aloysius F.

2003-01-01

Ternary single-source precursors were used to deposit CuInS2 thin films using chemical spray pyrolysis. We investigated the effect of the film composition on texture, secondary phase formation, and grain size. As-grown films were most often In-rich. They became more (204/220)-oriented as indium concentration increased, and always contained a yet unidentified secondary phase. The (112)-prefened orientation became more pronounced as the film composition became more Cu-rich. The secondary phase was determined to be an In-rich compound based on composition analysis and Raman spectroscopy. In addition, as-grown Cu-rich (112)-oriented films did not exhibit the In-rich compound. Depositing a thin Cu layer prior to the growth of CuInS2 increased the maximum grain size from - 0.5 micron to - 1 micron, and prevented the formation of the In-rich secondary phase.

Oxygen Isotopic Analyses of Water Extracted from the Martian Meteorite NWA 7034

NASA Astrophysics Data System (ADS)

Nunn, M.; Agee, C. B.; Thiemens, M. H.

2012-12-01

Introduction: The NWA 7034 meteorite has been identified as Martian, but it is distinct from the Shergottite-Nakhlite-Chassignite (SNC) grouping of meteorites in its petrology (it is the only known Martian basaltic breccia) and bulk silicate oxygen isotopic composition (Δ17O = 0.56 ± 0.06 ‰, where Δ17O = δ17O - 0.528 x δ18O, compared to the average SNC Δ17O ≈ 0.3 ‰) [e.g., 1-2]. We report here measurements of the oxygen isotopic composition of water extracted from NWA 7034 by stepwise heating. Methods: A piece (~1.2g) of NWA 7034 was pumped to vacuum until outgassing had stopped before heating to 50, 150, 320, 500, and 1000°C. The sample was maintained at each temperature step for at least one hour while collecting evolved volatiles in a liquid nitrogen cold trap. Water was selectively converted to molecular oxygen, the oxygen isotopic composition of which was then measured on a double collecting isotope ratio mass spectrometer. Results: Our stepwise heating experiments indicate NWA 7034 contains 3330ppm water, and this water has an average oxygen isotopic composition of Δ17O = 0.330 ± 0.011‰. The oxygen isotopic composition of water in NWA 7034 is unlike that of the silicates from which it is extracted (Δ17O = 0.56 ± 0.06 ‰) but is comparable to the average SNC silicate composition (Δ17O ≈ 0.3 ‰). However, there is no consensus on the oxygen isotopic composition of water in SNCs because aliquots of water extracted from different samples (separate pieces of a single meteorite or from different meteorites) have different oxygen isotopic compositions [3]. Furthermore, carbonates and sulfates extracted from SNCs also possess distinct oxygen isotopic compositions [4]. The variation in oxygen isotopic composition among these phases most likely results from the existence of isotopically distinct oxygen reservoirs on Mars that were not equilibrated. On Earth, interaction of ozone (O3) and carbon dioxide (CO2) leads to a mass independent oxygen isotopic composition of atmospheric CO2 [5]. This anomaly is transferred by exchange from CO2 to water and subsequently to secondary minerals. The much larger CO2 to water ratio on Mars could allow this process to introduce a measurable oxygen isotopic anomaly to sulfates, carbonates, and water. The magnitude and variability of this anomaly would depend on the formation mechanism of the species (particularly the source of oxygen), as is consistent with measurements to date of phases in SNCs. References: [1] Franchi, I.A., et al. (1999) MAPS 34, 657-661. [2] Rumble, D. and Irving, A.J. (2009) LPSC XXXX, #2293 [3] Karlsson, H.R., et al. (1992) Science 255, 1409-1411. [4] Farquhar, J. and Thiemens, M.H. (2000) J. Geophys. Res. 105, 11991-11997. [5] Yung, Y.L., et al. (1991) Geophys. Res. Lett. 18, 13-16.

Microstructure and mechanical properties investigation of in situ TiB2 and ZrB2 reinforced Al-4Cu composites

NASA Astrophysics Data System (ADS)

Lutfi Anis, Ahmad; Ramli, Rosmamuhammadani; Darham, Widyani; Zakaria, Azlan; Talari, Mahesh Kumar

2016-02-01

Conventional Al-Cu alloys exhibit coarse grain structure leading to inferior mechanical properties in as-cast condition. Expensive thermo-mechanical treatments are needed to improve microstructure and corresponding mechanical properties. In situ Al-based composites were developed to improve mechanical properties by dispersion strengthening and grain refinement obtained by the presence of particulates in the melt during solidification. In this work Al-4Cu - 3TiB2 and Al-4Cu-3ZrB2 in situ composites were prepared by liquid casting method. XRD, electron microscopy and mechanical tests were performed on suitably sectioned and metallographically prepared surfaces to investigate the phase distribution, hardness and tensile properties. It was found that the reinforcement particles were segregated along the grain boundaries of Al dendrites. Tensile fracture morphology for both Al-4Cu - 3TiB2 and Al-4Cu-3ZrB2 were analyzed and compared to determine the fracture propagation mechanism in the composites. Al-4Cu-3ZrB2 in situ composites displayed higher strength and hardness compared to Al-4Cu-3TiB2 which could be ascribed to the stronger interfacial bonding between the Al dendrites and ZrB2 particulates as evidenced from fractographs.

Downstream composition changes of acidic volcanic waters discharged into the Banyupahit stream, Ijen caldera, Indonesia

NASA Astrophysics Data System (ADS)

Delmelle, P.; Bernard, A.

2000-04-01

The crater lake of Kawah Ijen volcano contains extremely low pH (<0.4) waters with high SO4 (∼70000 mg/kg), Cl (∼21000 mg/kg), F (∼1500 mg/kg), Al (∼5000 mg/kg), Fe (∼2000 mg/kg) and trace metal (Cu ∼0.5, Zn ∼4, Pb ∼3 mg/kg) contents. These brines seep outward through the western crater rim and reappear on the other side as streamlets, which form the headwaters of the Banyupahit stream. The Banyupahit first mixes with fresh rivers and thermal springs in the Ijen caldera and then irrigates a coastal agricultural plain which is 30 km from the summit crater. We discuss the downstream composition changes affecting the Banyupahit waters by using stable isotope, chemical and mineralogical data collected from sites along the stream length. The saturation of the stream waters with respect to minerals was evaluated with SOLVEQ and WATEQ4F and compared with the geochemical observations. An aluminous mineralogy (alunogen, pickeringite, tamarugite and kalinite) develops in the upper part of the Banyupahit due to concentration of the headwaters by evaporation. Downstream attenuation of dissolved element concentrations results principally from dilution and from mineral precipitation. The stream pH changes from ∼0 at the source to >4 close to the mouth. The δD and δ18O values and the relative SO4-Cl-F contents of the Banyupahit waters indicate that the tributaries are mostly meteoric. Dissolved SO4 in the acidic stream come only from the crater lake seepages and are not involved later in microbially mediated reactions, as shown by their δ34S and δ18O values. Re-equilibration of the stream SO4 oxygen-isotope composition with H2O from tributaries does not occur. Calcium, SiO2, Al, Fe, K and SO4 behave non-conservatively in the stream waters. Gypsum, silica (amorphous or poorly ordered), a basic aluminum hydroxysulfate (basaluminite?), K-jarosite and amorphous ferric hydroxide may exert a solubility control on these elements along the entire stream length, or in certain stream sections, consistent with the thermochemical model results. Downstream concentration trends and mineral saturation levels suggest that precipitation of Sr-, Pb-rich barite and celestite consume Ba, Sr and Pb, whereas dissolved Cu, Pb and Zn may adsorb onto solid particles, especially after the junctions of the acidic stream with non-acidic rivers. We calculated that significant fluxes of SO4, F, Cl, Al, SiO2, Ti, Mn and Cu may reach the irrigation system, possibly causing serious environmental impacts such as soil acidification and induration.

Multi-biofunctional polymer graphene composite for bone tissue regeneration that elutes copper ions to impart angiogenic, osteogenic and bactericidal properties.

PubMed

Jaidev, L R; Kumar, Sachin; Chatterjee, Kaushik

2017-11-01

Despite several recent advances, poor vascularization in implanted scaffolds impedes complete regeneration for clinical success of bone tissue engineering. The present study aims to develop a multi-biofunctional nanocomposite for bone tissue regeneration using copper nanoparticle decorated reduced graphene oxide (RGO_Cu) hybrid particles in polycaprolactone (PCL) matrix (PCL/RGO_Cu). X-ray photoelectron spectroscopy and X-ray diffraction confirmed the presence of copper oxides (CuO and Cu 2 O) on RGO. Thermogravimetric analysis showed that 11.8% of copper was decorated on RGO. PCL/RGO_Cu exhibited steady release of copper ions in contrast to burst release from the composite containing copper alone (PCL/Cu). PCL/RGO_Cu exhibited highest modulus due to enhanced filler exfoliation. Endothelial cells rapidly proliferated on PCL/RGO_Cu confirming cytocompatibility. The sustained release of ions from PCL/RGO_Cu composites augmented tube formation by endothelial cells evidenced enhanced angiogenic activity. Gene expression of angiogenic markers VEGF and ANG-2 was higher on PCL/RGO_Cu compared to PCL. The osteogenic activity of PCL/RGO_Cu was confirmed by the 87% increase in mineral deposition by pre-osteoblasts compared to PCL. The bactericidal activity of PCL/RGO_Cu showed 78% reduction in viability of Escherichia coli. Thus, the multi-biofunctional PCL/RGO_Cu composite exhibits angiogenic, osteogenic and bactericidal properties, a step towards addressing some of the critical challenges in bone tissue engineering. Copyright © 2017 Elsevier B.V. All rights reserved.

Microstructure and mechanical properties of aluminium matrix composites reinforced by Al{sub 62}Cu{sub 25.5}Fe{sub 12.5} melt spun ribbon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lityńska-Dobrzyńska, Lidia, E-mail: l.litynska@imim.pl; Mitka, Mikołaj; Góral, Anna

Aluminium matrix composites containing 15, 30 and 50 vol.% of pulverized Al{sub 62}Cu{sub 25.5}Fe{sub 12.5} (in at.%) melt spun ribbons have been prepared by a vacuum hot pressing (T = 673 K, P = 600 MPa). The microstructure of the initial ribbon and the composites was investigated using X-ray, scanning and transmission electron microscopy. In the as-spun ribbon the quasicrystalline icosahedral phase (i-phase) coexisted with the cubic copper rich β-Al(Cu, Fe) intermetallic compound. The phase composition of Al-Cu-Fe particles changed after consolidation process and the i-phase transformed partially to the ω-Al{sub 70}Cu{sub 20}Fe{sub 10} phase. Additionally, the Θ-Al{sub 2}Cu phasemore » formed at the α(Al)/Al-Cu-Fe particle interfaces. With an increase in volume fraction of the reinforcement the hardness of the composites increased up to HV = 180 for the highest amount of added particles. The ultimate compression strength of the same sample reached the value of 545 MPa. - Highlights: • Al and 15, 30, 50% of pulverized Al{sub 62}Cu{sub 25.5}Fe{sub 12.5} melt spun ribbon were consolidated. • The initial ribbon consisted of the icosahedral i-phase and copper rich β-Al(Cu, Fe). • The i-phase partially transforms to ω-Al{sub 7}Cu{sub 2}Fe phase in all composites. • Increase of microhardness and compressive strength with content of reinforcement • Ultimate compression strength 545 MPa for 50% of added particles.« less

Facile synthesis of uniform hierarchical composites CuO-CeO2 for enhanced dye removal

NASA Astrophysics Data System (ADS)

Xu, Pan; Niu, Helin; Chen, Jingshuai; Song, Jiming; Mao, Changjie; Zhang, Shengyi; Gao, Yuanhao; Chen, Changle

2016-12-01

The hierarchically shaped CuO-CeO2 composites were prepared through a facile solvothermal method without using any template. The as-prepared products were characterized by X-ray powder diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, and N2 adsorption-desorption analysis. In the characterization, we found that CuO-CeO2 composites were showed uniform size and morphology which were consisted of the secondary nanoflakes interconnected with each other. Most interestingly, the composites showed efficient performance to remove methyl blue and Congo red dyes from water with maximum adsorption capacities of 2131.24 and 1072.09 mg g-1, respectively. In addition, because of their larger surface area and the unique hierarchical structures, the adsorption performance of the CuO-CeO2 composites is much better than the materials of CuO and CeO2.

Isotopic Resonance Hypothesis: Experimental Verification by Escherichia coli Growth Measurements

NASA Astrophysics Data System (ADS)

Xie, Xueshu; Zubarev, Roman A.

2015-03-01

Isotopic composition of reactants affects the rates of chemical and biochemical reactions. As a rule, enrichment of heavy stable isotopes leads to progressively slower reactions. But the recent isotopic resonance hypothesis suggests that the dependence of the reaction rate upon the enrichment degree is not monotonous. Instead, at some ``resonance'' isotopic compositions, the kinetics increases, while at ``off-resonance'' compositions the same reactions progress slower. To test the predictions of this hypothesis for the elements C, H, N and O, we designed a precise (standard error +/-0.05%) experiment that measures the parameters of bacterial growth in minimal media with varying isotopic composition. A number of predicted resonance conditions were tested, with significant enhancements in kinetics discovered at these conditions. The combined statistics extremely strongly supports the validity of the isotopic resonance phenomenon (p << 10-15). This phenomenon has numerous implications for the origin of life studies and astrobiology, and possible applications in agriculture, biotechnology, medicine, chemistry and other areas.

Investigation on the properties of nano copper matrix composite via vacuum arc melting method

NASA Astrophysics Data System (ADS)

Liu, Yi; Leng, Jinfeng; Wu, Qirui; Zhang, Shaochen; Teng, Xinying

2017-10-01

Copper and copper matrix composites (CMCs) are widely used as electrical contact materials in electrical switch systems due to their excellent electrical properties. Graphene has great mechanical, physical and electrical properties, which is competent as an attractive reinforcing material for fabricating CMCs. Therefore, graphene was added to CMCs to improve the mechanical properties. In this study, graphene-reinforced copper matrix composites (Gr/Cu composites) were obtained. The xGr/Cu (x  =  0, 0.1, 0.3 and 0.5 wt.%) composites were fabricated via the vacuum arc melting method and compared the performance of them. The mechanical properties and electrical properties were obtained by measuring the hardness and conductivity. The microstructure of Gr/Cu composites was observed by optical microscopy (OM) and scanning electron microscopy (SEM). With the addition of graphene from 0 wt.% to 0.5 wt.%, the densities of materials decreased from 97.0% to 95.7%. With the increasing of graphene content, the hardness of composites increased at beginning and then decreased. In this range of adding amount, the hardness of 0.3Gr/Cu composite was up to 66.8 HB and increased by 15.4% compared to Al2O3/Cu composites without graphene. With the addition of graphene powder, the international annealing copper standard IACS% of Gr/Cu composites decreased from 86.16 to 69.86. The range of decline and the percentage of decline range are middle and 18.9%, respectively.

[Sources of Methane in the Boreal Region

NASA Technical Reports Server (NTRS)

1998-01-01

In determining the global methane budget the sources of methane must be balanced with the sinks and atmospheric inventory. The approximate contribution of the different methane sources to the budget has been establish showing the major terrestrial inputs as rice, wetlands, bogs, fens, and tundra. Measurements and modeling of production in these sources suggest that temperature, water table height and saturation along with substratum composition are important in controlling methane production and emission. The isotopic budget of 13 C and D/H in methane can be used as a tool to clarify the global budget. This approach has achieved success at constraining the inputs. Studies using the isotopic approach place constraints on global methane production from different sources. Also, the relation between the two biogenic production pathways, acetate fermentation and CO2 reduction, and the effect of substratum composition can be made using isotope measurements shows the relation between the different biogenic, thermogenic and anthropogenic sources of methane as a function of the carbon and hydrogen isotope values for each source and the atmosphere, tropospheric composition. Methane emissions from ponds and fens are a significant source in the methane budget of the boreal region. An initial study in 1993 and 1994 on the isotopic composition of this methane source and the isotopic composition in relation to oxidation of methane at the sediment surface of the ponds or fen was conducted as part of our BOREAS project. The isotopic composition of methane emitted by saturated anoxic sediment is dependent on the sediment composition and geochemistry, but will be influenced by in situ oxidation, in part, a function of rooted plant activity. The influence of oxidation mediated by rooted plant activities on the isotopic composition of methane is not well known and will depend on the plant type, sediment temperature, and numerous other variables. Information on this isotopic composition is important in both understanding the bio-geochemistry of the system and also in determining the regional and global inputs for the methane isotope budget. In determining the destruction of methane for balancing the atmospheric methane budget soil oxidation must be considered.

Iron isotopic composition of blood serum in anemia of chronic kidney disease.

PubMed

Anoshkina, Yulia; Costas-Rodríguez, Marta; Speeckaert, Marijn; Van Biesen, Wim; Delanghe, Joris; Vanhaecke, Frank

2017-05-24

Chronic kidney disease (CKD) is a general term for disorders that affect the structure and function of the kidneys. Iron deficiency (ID) and anemia occur in the vast majority of CKD patients, most of whom are elderly. However, establishing the cause of anemia in CKD, and therefore making an informed decision concerning the corresponding therapeutic treatment, is still a challenge. High-precision Fe isotopic analysis of blood serum samples of CKD patients with and without ID/anemia was performed via multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS) for such a purpose. Patients with CKD and/or iron disorders showed a heavier serum Fe isotopic composition than controls. Many clinical parameters used for the diagnosis and follow-up of anemia correlated significantly with the serum Fe isotopic composition. In contrast, no relation was observed between the serum Fe isotopic composition and the estimated glomerular filtration rate as a measure of kidney function. Among the CKD patients, the serum Fe isotopic composition was substantially heavier in the occurrence of ID anemia, while erythropoietin-related anemia did not exert this effect. The Fe isotopic composition can thus be useful for distinguishing these different types of anemias in CKD patients, i.e. ID anemia vs. erythropoietin-related anemia.

Cu@C nanoporous composites containing little copper oxides derived from dimethyl imidazole modified MOF199 as electrocatalysts for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Wei, Xuedong; Li, Na; Zhang, Xianming

2017-12-01

It remains a huge challenge to develop non precious electrocatalysts with high activity to substitute commercial Pt catalysts for hydrogen evolution reactions (HER). Here, the C-Cu-DI and C-Cu materials with the copper based nanoporous carbon structures were synthesized by carbonizing MOF199 and DI-MOF199. The composite structure and HER electrocatalytic properties of the C-Cu-DI and C-Cu materials are studied. The results show that C-Cu-DI and C-Cu samples exhibit good catalytic activity. And C-Cu-DI sample through the addition of Dimethyl imidazole(DI) in the DI-MOF199 precursor has higher electrocatalytic activity than the C-Cu sample. The superior catalytic activity is attributed to the special composite structure of nanoscale deposition particles on the framework with plenty of nano pores and nano copper and few copper oxidation particles distributed or wrapped into the amorphous porous carbon phase. The nano copper and few copper oxidation particles in the C-Cu and C-Cu-DI catalysts maybe provide the more effective catalytic activity sites. The C-Cu-DI composite with large size spherical hollow deposition particles has higher conductivity, better BET surface area and reasonable micro-meso-macro porous distribution, so the overpotentials at the current density of 1 mA cm-2 and 10 mA cm-2 are respectively 270 mV and 390 mV vs. RHE. Although the HER activity has a big gap with commercial platinum catalyst, this study can provide an important experimental exploration for the design of copper based non noble metal/nano porous carbon composite HER electrocatalyst.

Xenon isotopic composition of the Mid Ocean Ridge Basalt (MORB) source

NASA Astrophysics Data System (ADS)

Peto, M. K.; Mukhopadhyay, S.

2012-12-01

Although convection models do not preclude preservation of smaller mantle regions with more pristine composition throughout Earth's history, it has been widely assumed that the moon forming giant impact likely homogenizes the whole mantle following a magma ocean that extended all the way to the bottom of the mantle. Recent findings of tungsten and xenon heterogeneities in the mantle [1,2,3,4], however, imply that i) the moon forming giant impact may not have homogenized the whole mantle and ii) plate tectonics was inefficient in erasing early formed compositional differences, particularly for the xenon isotopes. Therefore, the xenon isotope composition in the present day mantle still preserves a memory of early Earth processes. However, determination of the xenon isotopic composition of the mantle source is still scarce, since the mantle composition is overprinted by post-eruptive atmospheric contamination in basalts erupted at ocean islands and mid ocean ridges. The xenon composition of the depleted upper mantle has been defined by the gas rich sample, 2πD43 (also known as "popping rock"), from the North Atlantic (13° 469`N). However, the composition of a single sample is not likely to define the composition of the upper mantle, especially since popping rock has an "enriched" trace element composition. We will present Ne, Ar and Xe isotope data on MORB glass samples with "normal" helium isotope composition (8±1 Ra) from the Southeast Indian Ridge, the South Atlantic Ridge, the Sojourn Ridge, the Juan de Fuca, the East Pacific Rise, and the Gakkel Ridge. Following the approach of [1], we correct for syn- and post-eruptive atmosphere contamination, and determine the variation of Ar and Xe isotope composition of the "normal" MORB source. We investigate the effect of atmospheric recycling in the variation of MORB mantle 40Ar/36Ar and 129Xe/130Xe ratios, and attempt to constrain the average upper mantle argon and xenon isotopic compositions. [1] Mukhopadhyay, Nature 2012; [2] Tucker et al., EPSL (in review); [3] Moreira et al., Nature 1998 [4] Touboul et al., Science 2012.

Modelling and intepreting the isotopic composition of water vapour in convective updrafts

NASA Astrophysics Data System (ADS)

Bolot, M.; Legras, B.; Moyer, E. J.

2012-08-01

The isotopic compositions of water vapour and its condensates have long been used as tracers of the global hydrological cycle, but may also be useful for understanding processes within individual convective clouds. We review here the representation of processes that alter water isotopic compositions during processing of air in convective updrafts and present a unified model for water vapour isotopic evolution within undiluted deep convective cores, with a special focus on the out-of-equilibrium conditions of mixed phase zones where metastable liquid water and ice coexist. We use our model to show that a combination of water isotopologue measurements can constrain critical convective parameters including degree of supersaturation, supercooled water content and glaciation temperature. Important isotopic processes in updrafts include kinetic effects that are a consequence of diffusive growth or decay of cloud particles within a supersaturated or subsaturated environment; isotopic re-equilibration between vapour and supercooled droplets, which buffers isotopic distillation; and differing mechanisms of glaciation (droplet freezing vs. the Wegener-Bergeron-Findeisen process). As all of these processes are related to updraft strength, droplet size distribution and the retention of supercooled water, isotopic measurements can serve as a probe of in-cloud conditions of importance to convective processes. We study the sensitivity of the profile of water vapour isotopic composition to differing model assumptions and show how measurements of isotopic composition at cloud base and cloud top alone may be sufficient to retrieve key cloud parameters.

Modelling and interpreting the isotopic composition of water vapour in convective updrafts

NASA Astrophysics Data System (ADS)

Bolot, M.; Legras, B.; Moyer, E. J.

2013-08-01

The isotopic compositions of water vapour and its condensates have long been used as tracers of the global hydrological cycle, but may also be useful for understanding processes within individual convective clouds. We review here the representation of processes that alter water isotopic compositions during processing of air in convective updrafts and present a unified model for water vapour isotopic evolution within undiluted deep convective cores, with a special focus on the out-of-equilibrium conditions of mixed-phase zones where metastable liquid water and ice coexist. We use our model to show that a combination of water isotopologue measurements can constrain critical convective parameters, including degree of supersaturation, supercooled water content and glaciation temperature. Important isotopic processes in updrafts include kinetic effects that are a consequence of diffusive growth or decay of cloud particles within a supersaturated or subsaturated environment; isotopic re-equilibration between vapour and supercooled droplets, which buffers isotopic distillation; and differing mechanisms of glaciation (droplet freezing vs. the Wegener-Bergeron-Findeisen process). As all of these processes are related to updraft strength, particle size distribution and the retention of supercooled water, isotopic measurements can serve as a probe of in-cloud conditions of importance to convective processes. We study the sensitivity of the profile of water vapour isotopic composition to differing model assumptions and show how measurements of isotopic composition at cloud base and cloud top alone may be sufficient to retrieve key cloud parameters.

Isotope effects on the optical spectra of semiconductors

NASA Astrophysics Data System (ADS)

Cardona, Manuel; Thewalt, M. L. W.

2005-10-01

Since the end of the cold war, macroscopic amounts of separated stable isotopes of most elements have been available “off the shelf” at affordable prices. Using these materials, single crystals of many semiconductors have been grown and the dependence of their physical properties on isotopic composition has been investigated. The most conspicuous effects observed have to do with the dependence of phonon frequencies and linewidths on isotopic composition. These affect the electronic properties of solids through the mechanism of electron-phonon interaction, in particular, in the corresponding optical excitation spectra and energy gaps. This review contains a brief introduction to the history, availability, and characterization of stable isotopes, including their many applications in science and technology. It is followed by a concise discussion of the effects of isotopic composition on the vibrational spectra, including the influence of average isotopic masses and isotopic disorder on the phonons. The final sections deal with the effects of electron-phonon interaction on energy gaps, the concomitant effects on the luminescence spectra of free and bound excitons, with particular emphasis on silicon, and the effects of isotopic composition of the host material on the optical transitions between the bound states of hydrogenic impurities.

Determination of lithium isotopes at natural abundance levels by atomic absorption spectrometry

USGS Publications Warehouse

Meier, A.L.

1982-01-01

The relationships of the absorption of 6Li and 7Li hollow cathode lamp emissions are used to determine lithium isotopic composition in the natural abundance range of geologic materials. Absorption was found to have a nonlinear dependence upon total lithium concentration and isotopic composition. A method using nonlinear equations to describe the relationship of the absorption of 6Li and 7Li lamp radiation is proposed as a means of calculating isotopic composition that is independent of total lithium concentration.

Implementation of a solid target production facility

NASA Astrophysics Data System (ADS)

Tochon-Danguy, H. J.; Poniger, S. S.; Sachinidis, J. I.; Panopoulos, H. P.; Scott, A. M.

2012-12-01

The desire to utilize long-lived PET isotopes in Australia has significantly increased over the years and several research projects for labelling of peptides, proteins and biomolecules, including labelling of recombinant antibodies has been restricted due to the limited availability of suitable isotopes. This need has led to the recent installation and commissioning of a new facility dedicated to fully automated solid target isotope production, including 24I, 64Cu, 89Zr and 86Y at the Austin Health Centre for PET.

Chemical separation and mass spectrometry of Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial materials using thermal ionization mass spectrometry.

PubMed

Yamakawa, Akane; Yamashita, Katsuyuki; Makishima, Akio; Nakamura, Eizo

2009-12-01

A sequential chemical separation technique for Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial silicate rocks was developed for precise and accurate determination of elemental concentration by the isotope dilution method (ID). The technique uses a combination of cation-anion exchange chromatography and Eichrom nickel specific resin. The method was tested using a variety of matrixes including bulk meteorite (Allende), terrestrial peridotite (JP-1), and basalt (JB-1b). Concentrations of each element was determined by thermal ionization mass spectrometry (TIMS) using W filaments and a Si-B-Al type activator for Cr, Fe, Ni, and Zn and a Re filament and silicic acid-H3PO4 activator for Cu. The method can be used to precisely determine the concentrations of these elements in very small silicate samples, including meteorites, geochemical reference samples, and mineral standards for microprobe analysis. Furthermore, the Cr mass spectrometry procedure developed in this study can be extended to determine the isotopic ratios of 53Cr/52Cr and 54Cr/52Cr with precision of approximately 0.05epsilon and approximately 0.10epsilon (1epsilon = 0.01%), respectively, enabling cosmochemical applications such as high precision Mn-Cr chronology and investigation of nucleosynthetic isotopic anomalies in meteorites.

Latitudinal change in precipitation and water vapor isotopes over Southern ocean

NASA Astrophysics Data System (ADS)

Rahul, P.

2015-12-01

The evaporation process over ocean is primary source of water vapor in the hydrological cycle. The Global Network of Isotopes in Precipitation (GNIP) dataset of rainwater and water vapor isotopes are predominantly based on continental observations, with very limited observation available from the oceanic area. Stable isotope ratios in precipitation provide valuable means to understand the process of evaporation and transport of water vapor. This is further extended in the study of past changes in climate from the isotopic composition of ice core. In this study we present latitudinal variability of water vapor and rainwater isotopic composition and compared it with factors like physical condition of sea surface water from near equator (1°S) to the polar front (56°S) during the summer time expedition of the year 2013. The water vapor and rainwater isotopes showed a sharp depletion in isotopes while progressively move southward from the tropical regions (i.e. >30°S), which follows the pattern recorded in the surface ocean water isotopic composition. From the tropics to the southern latitudes, the water vapor d18O varied between -11.8‰ to -14.7‰ while dD variation ranges between -77.7‰ to -122.2‰. Using the data we estimated the expected water vapor isotopic composition under kinetic as well as equilibrium process. Our observation suggests that the water vapor isotopic compositions are in equilibrium with the sea water in majority of cases. At one point of observation, where trajectory of air parcel originated from the continental region, we observed a large deviation from the existing trend of latitudinal variability. The deduced rainwater composition adopting equilibrium model showed a consistent pattern with observed values at the tropical region, while role of kinetic process become dominant on progressive shift towards the southern latitudes. We will draw comparison of our observation with other data available in the literature together with isotope model data during the presentation.

Stable Isotope Anatomy of Tropical Cyclone Ita, North-Eastern Australia, April 2014

PubMed Central

Munksgaard, Niels C.; Zwart, Costijn; Kurita, Naoyuki; Bass, Adrian; Nott, Jon; Bird, Michael I.

2015-01-01

The isotope signatures registered in speleothems during tropical cyclones (TC) provides information about the frequency and intensity of past TCs but the precise relationship between isotopic composition and the meteorology of TCs remain uncertain. Here we present continuous δ18O and δ2H data in rainfall and water vapour, as well as in discrete rainfall samples, during the passage of TC Ita and relate the evolution in isotopic compositions to local and synoptic scale meteorological observations. High-resolution data revealed a close relationship between isotopic compositions and cyclonic features such as spiral rainbands, periods of stratiform rainfall and the arrival of subtropical and tropical air masses with changing oceanic and continental moisture sources. The isotopic compositions in discrete rainfall samples were remarkably constant along the ~450 km overland path of the cyclone when taking into account the direction and distance to the eye of the cyclone at each sampling time. Near simultaneous variations in δ18O and δ2H values in rainfall and vapour and a near-equilibrium rainfall-vapour isotope fractionation indicates strong isotopic exchange between rainfall and surface inflow of vapour during the approach of the cyclone. In contrast, after the passage of spiral rainbands close to the eye of the cyclone, different moisture sources for rainfall and vapour are reflected in diverging d-excess values. High-resolution isotope studies of modern TCs refine the interpretation of stable isotope signatures found in speleothems and other paleo archives and should aim to further investigate the influence of cyclone intensity and longevity on the isotopic composition of associated rainfall. PMID:25742628

Elemental and iron isotopic composition of aerosols collected in a parking structure.

PubMed

Majestic, Brian J; Anbar, Ariel D; Herckes, Pierre

2009-09-01

The trace metal contents and iron isotope composition of size-resolved aerosols were determined in a parking structure in Tempe, AZ, USA. Particulate matter (PM)<2.5 microm in diameter (the fine fraction) and PM>2.5 microm were collected. Several air toxics (e.g., arsenic, cadmium, and antimony) were enriched above the crustal average, implicating automobiles as an important source. Extremely high levels of fine copper (up to 1000 ng m(-3)) were also observed in the parking garage, likely from brake wear. The iron isotope composition of the aerosols were found to be +0.15+/-0.03 per thousand and +0.18+/-0.03 per thousand for the PM<2.5 microm and PM>2.5 microm fractions, respectively. The similarity of isotope composition indicates a common source for each size fraction. To better understand the source of iron in the parking garage, the elemental composition in four brake pads (two semi-metallic and two ceramic), two tire tread samples, and two waste oil samples were determined. Striking differences in the metallic and ceramic brake pads were observed. The ceramic brake pads contained 10-20% copper by mass, while the metallic brake pads contained about 70% iron, with very little copper. Both waste oil samples contained significant amounts of calcium, phosphorous, and zinc, consistent with the composition of some engine oil additives. Differences in iron isotope composition were observed between the source materials; most notably between the tire tread (average=+0.02 per thousand) and the ceramic brake linings (average=+0.65 per thousand). Differences in isotopic composition were also observed between the metallic (average=+0.18 per thousand) and ceramic brake pads, implying that iron isotope composition may be used to resolve these sources. The iron isotope composition of the metallic brake pads was found to be identical to the aerosols, implying that brake dust is the dominant source of iron in a parking garage.

Intramolecular Isotopic Studies: Chemical Enhancements and Alternatives

NASA Astrophysics Data System (ADS)

Hayes, J. M.

2016-12-01

As mass spectroscopic and NMR-based methods now appropriately flourish, chemical techniques should not be forgotten. First, the methods developed by pioneering intramolecular analysts can be reapplied to new samples. Second, they can be extended. The synthesis of intramolecular isotopic standards is particularly important and straightforward. It requires only that a chemical reaction has no secondary products. An example is provided by the addition of carbon dioxide to a Grignard reagent. The reaction proceeds with an isotope effect. The isotopic composition of the carboxyl group in the acid which is produced is thus not equal to that of the starting carbon dioxide but the unconsumed CO2 can be recovered and analyzed. A simple titration can show that all the rest of the CO2 is in the product acid. The isotopic composition of the carboxyl group can then be calculated by difference. The product is an intramolecular isotopic standard, an organic molecule in which the isotopic composition of a specific carbon position is known accurately. Both analysts and reviewers can thus gain invaluable confidence in the accuracy of instrumental results. A second example: the haloform reaction quantitatively degrades methyl ketones, producing a carboxylic acid which can be decarboxylated to determine the isotopic composition of the parent carbonyl and a haloform (CHI3, for example) that can be combusted to determine the isotopic composition of the methyl group. Ketones thus analyzed can be combined with Grignard reagents to yield carbon skeletons in which the isotopic compositions of internal and terminal -CH2- and -CH3 groups are known accurately. In general, analysts accustomed to demanding quantitative reactions should remember the power of mass balances and recognize that many organic-chemical reactions, while not quantitative, lack side products and can be driven to the total consumption of at least one reactant.

Testing the chondrule-rich accretion model for planetary embryos using calcium isotopes

NASA Astrophysics Data System (ADS)

Amsellem, Elsa; Moynier, Frédéric; Pringle, Emily A.; Bouvier, Audrey; Chen, Heng; Day, James M. D.

2017-07-01

Understanding the composition of raw materials that formed the Earth is a crucial step towards understanding the formation of terrestrial planets and their bulk composition. Calcium is the fifth most abundant element in terrestrial planets and, therefore, is a key element with which to trace planetary composition. However, in order to use Ca isotopes as a tracer of Earth's accretion history, it is first necessary to understand the isotopic behavior of Ca during the earliest stages of planetary formation. Chondrites are some of the oldest materials of the Solar System, and the study of their isotopic composition enables understanding of how and in what conditions the Solar System formed. Here we present Ca isotope data for a suite of bulk chondrites as well as Allende (CV) chondrules. We show that most groups of carbonaceous chondrites (CV, CI, CR and CM) are significantly enriched in the lighter Ca isotopes (δ 44 / 40 Ca = + 0.1 to + 0.93 ‰) compared with bulk silicate Earth (δ 44 / 40 Ca = + 1.05 ± 0.04 ‰, Huang et al., 2010) or Mars, while enstatite chondrites are indistinguishable from Earth in Ca isotope composition (δ 44 / 40 Ca = + 0.91 to + 1.06 ‰). Chondrules from Allende are enriched in the heavier isotopes of Ca compared to the bulk and the matrix of the meteorite (δ 44 / 40 Ca = + 1.00 to + 1.21 ‰). This implies that Earth and Mars have Ca isotope compositions that are distinct from most carbonaceous chondrites but that may be like chondrules. This Ca isotopic similarity between Earth, Mars, and chondrules is permissive of recent dynamical models of planetary formation that propose a chondrule-rich accretion model for planetary embryos.

Growth of Cu2ZnSnSe4 Film under Controllable Se Vapor Composition and Impact of Low Cu Content on Solar Cell Efficiency.

PubMed

Li, Jianjun; Wang, Hongxia; Wu, Li; Chen, Cheng; Zhou, Zhiqiang; Liu, Fangfang; Sun, Yun; Han, Junbo; Zhang, Yi

2016-04-27

It is a challenge to fabricate high quality Cu2ZnSnSe4 (CZTSe) film with low Cu content (Cu/(Zn + Sn) < 0.8). In this work, the growth mechanisms of CZTSe films under different Se vapor composition are investigated by DC-sputtering and a postselenization approach. The composition of Se vapor has important influence on the compactability of the films and the diffusion of elements in the CZTSe films. By adjusting the composition of Se vapor during the selenization process, an optimized two step selenization process is proposed and highly crystallized CZTSe film with low Cu content (Cu/(Zn + Sn) = 0.75) is obtained. Further study of the effect of Cu content on the morphology and photovoltaic performance of the corresponding CZTSe solar cells has shown that the roughness of the CZTSe absorber film increases when Cu content decreases. As a consequence, the reflection loss of CZTSe solar cells reduces dramatically and the short circuit current density of the cells improve from 34.7 mA/cm(2) for Cu/(Zn + Sn) = 0.88 to 38.5 mA/cm(2) for Cu/(Zn + Sn) = 0.75. In addition, the CZTSe solar cells with low Cu content show longer minority carrier lifetime and higher open circuit voltage than the high Cu content devices. A champion performance CZTSe solar cell with 10.4% efficiency is fabricated with Cu/(Zn + Sn) = 0.75 in the CZTSe film without antireflection coating.

Non-destructive measurement of carbonic anhydrase activity and the oxygen isotope composition of soil water

NASA Astrophysics Data System (ADS)

Jones, Sam; Sauze, Joana; Ogée, Jérôme; Wohl, Steven; Bosc, Alexandre; Wingate, Lisa

2016-04-01

Carbonic anhydrases are a group of metalloenzymes that catalyse the hydration of aqueous carbon dioxide (CO2). The expression of carbonic anhydrase by bacteria, archaea and eukarya has been linked to a variety of important biological processes including pH regulation, substrate supply and biomineralisation. As oxygen isotopes are exchanged between CO2 and water during hydration, the presence of carbonic anhydrase in plants and soil organisms also influences the oxygen isotope budget of atmospheric CO2. Leaf and soil water pools have distinct oxygen isotope compositions, owing to differences in pool sizes and evaporation rates, which are imparted on CO2during hydration. These differences in the isotopic signature of CO2 interacting with leaves and soil can be used to partition the contribution of photosynthesis and soil respiration to net terrestrial CO2 exchange. However, this relies on our knowledge of soil carbonic anhydrase activity and currently, the prevalence and function of these enzymes in soils is poorly understood. Isotopic approaches used to estimate soil carbonic anhydrase activity typically involve the inversion of models describing the oxygen isotope composition of CO2 fluxes to solve for the apparent, potentially catalysed, rate of oxygen exchange during hydration. This requires information about the composition of CO2 in isotopic equilibrium with soil water obtained from destructive, depth-resolved soil water sampling. This can represent a significant challenge in data collection given the considerable potential for spatial and temporal variability in the isotopic composition of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by constraining carbonic anhydrase activity and the composition of soil water in isotopic equilibrium with CO2 by solving simultaneously the mass balance for two soil CO2 steady states differing only in the oxygen isotope composition of ambient CO2. This non-destructive approach was tested through laboratory incubations of air-dried soils that were re-wetted with water of known isotopic composition. Performance was assessed by comparing estimates of the soil water oxygen isotope composition derived from open chamber flux measurements with those measured in the irrigation water and soil water extracted following incubations. The influence of soil pH and bovine carbonic anhydrase additions on these estimates was also investigated. Coherent values were found between the soil water composition estimates obtained from the dual steady state approach and those measured for irrigation waters. Estimates of carbonic anhydrase activity made using this approach also reflected well artificial increases to the concentration of carbonic anhydrase and indicated that this activity was sensitive to soil pH.

Multiple stable isotope fronts during non-isothermal fluid flow

NASA Astrophysics Data System (ADS)

Fekete, Szandra; Weis, Philipp; Scott, Samuel; Driesner, Thomas

2018-02-01

Stable isotope signatures of oxygen, hydrogen and other elements in minerals from hydrothermal veins and metasomatized host rocks are widely used to investigate fluid sources and paths. Previous theoretical studies mostly focused on analyzing stable isotope fronts developing during single-phase, isothermal fluid flow. In this study, numerical simulations were performed to assess how temperature changes, transport phenomena, kinetic vs. equilibrium isotope exchange, and isotopic source signals determine mineral oxygen isotopic compositions during fluid-rock interaction. The simulations focus on one-dimensional scenarios, with non-isothermal single- and two-phase fluid flow, and include the effects of quartz precipitation and dissolution. If isotope exchange between fluid and mineral is fast, a previously unrecognized, significant enrichment in heavy oxygen isotopes of fluids and minerals occurs at the thermal front. The maximum enrichment depends on the initial isotopic composition of fluid and mineral, the fluid-rock ratio and the maximum change in temperature, but is independent of the isotopic composition of the incoming fluid. This thermally induced isotope front propagates faster than the signal related to the initial isotopic composition of the incoming fluid, which forms a trailing front behind the zone of transient heavy oxygen isotope enrichment. Temperature-dependent kinetic rates of isotope exchange between fluid and rock strongly influence the degree of enrichment at the thermal front. In systems where initial isotope values of fluids and rocks are far from equilibrium and isotope fractionation is controlled by kinetics, the temperature increase accelerates the approach of the fluid to equilibrium conditions with the host rock. Consequently, the increase at the thermal front can be less dominant and can even generate fluid values below the initial isotopic composition of the input fluid. As kinetics limit the degree of isotope exchange, a third front may develop in kinetically limited systems, which propagates with the advection speed of the incoming fluid and is, therefore, traveling fastest. The results show that oxygen isotope signatures at thermal fronts recorded in rocks and veins that experienced isotope exchange with fluids can easily be misinterpreted, namely if bulk analytical techniques are applied. However, stable isotope microanalysis on precipitated minerals may - if later isotope exchange is kinetically limited - provide a valuable archive of the transient thermal and hydrological evolution of a system.

Development and characterization of laser surface cladding (Ti,W)C reinforced Ni-30Cu alloy composite coating on copper

NASA Astrophysics Data System (ADS)

Yan, Hua; Zhang, Peilei; Yu, Zhishui; Li, Chonggui; Li, Ruidi

2012-07-01

To improve the wear resistance of copper components, laser surface cladding (LSC) was applied to deposit (Ti,W)C reinforced Ni-30Cu alloy composite coating on copper using a cladding interlayer of Ni-30Cu alloy by Nd:YAG laser. The microstructure and phases of the composite coating were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray energy dispersive microanalysis (EDX). Microhardness tester and pin-on-disc wear tester were employed to evaluate the hardness and dry-sliding wear resistance. The results show that crack-free composite coating with metallurgical bonding to the copper substrate is obtained. Phases identified in the (Ti,W)C-reinforced Ni-30Cu alloy composite layer are composed of TiWC2 reinforcements and (Ni,Cu) solid solution. TiWC2 reinforcements are distributed uniformly in the (Ni,Cu) solid solution matrix with dendritic morphology in the upper region and with particles in the mid-lower region. The microhardness and wear properties of the composite coating are improved significantly in comparison to the as-received copper substrate due to the addition of 50 wt% (Ti,W)C multicarbides.

Microscopic model for the isotope effect in the high-Tc oxides

NASA Astrophysics Data System (ADS)

Kresin, V. Z.; Wolf, S. A.

1994-02-01

An unconventional microscopic mechanism relating Tc and the isotope substitution for the doped superconductors such as the high-Tc oxides is proposed. Strong nonadiabaticity, when it is impossible, strictly speaking, to separate fully the nuclear and electronic degrees of freedom, leads to a peculiar dependence of the carrier concentration n on the ionic mass M. This case corresponds, for example, to the isotopic substitution of the axial oxygen in YBa2Cu3O7-x. Because of the dependence of Tc on n, this leads to the dependence of Tc on M, that is to the isotope effect. The minimum value of the isotope coefficient corresponds to Tc=Tmaxc.

Using multiple isotopes to understand the source of ingredients used in golden beverages

NASA Astrophysics Data System (ADS)

Wynn, J. G.

2011-12-01

Traditionally, beer contains 4 simple ingredients: water, barley, hops and yeast. Each of these ingredients used in the brewing process contributes some combination of a number of "traditional" stable isotopes (i.e., isotopes of H, C, O, N and S) to the final product. As an educational exercise in an "Analytical Techniques in Geology" course, a group of students analyzed the isotopic composition of the gas, liquid and solid phases of a variety of beer samples collected from throughout the world (including other beverages). The hydrogen and oxygen isotopic composition of the water followed closely the isotopic composition of local meteoric water at the source of the brewery, although there is a systematic offset from the global meteoric water line that may be due to the effects of CO2-H2O equilibration. The carbon isotopic composition of the CO2 reflected that of the solid residue (the source of carbon used as a fermentation substrate), but may potentially be modified by addition of gas-phase CO2 from an inorganic source. The carbon isotopic composition of the solid residue similarly tracks that of the fermentation substrate, and may indicate some alcohol fermented from added sugars in some cases. The nitrogen isotopic composition of the solid residue was relatively constant, and may track the source of nitrogen in the barley, hops and yeast. Each of the analytical methods used is a relatively standard technique used in geological applications, making this a "fun" exercise for those involved, and gives the students hands-on experience with a variety of analytes from a non-traditional sample material.

The ruthenium isotopic composition of the oceanic mantle

NASA Astrophysics Data System (ADS)

Bermingham, K. R.; Walker, R. J.

2017-09-01

The approximately chondritic relative, and comparatively high absolute mantle abundances of the highly siderophile elements (HSE), suggest that their concentrations in the bulk silicate Earth were primarily established during a final ∼0.5 to 1% of ;late accretion; to the mantle, following the cessation of core segregation. Consequently, the isotopic composition of the HSE Ru in the mantle reflects an amalgamation of the isotopic compositions of late accretionary contributions to the silicate portion of the Earth. Among cosmochemical materials, Ru is characterized by considerable mass-independent isotopic variability, making it a powerful genetic tracer of Earth's late accretionary building blocks. To define the Ru isotopic composition of the oceanic mantle, the largest portion of the accessible mantle, we report Ru isotopic data for materials from one Archean and seven Phanerozoic oceanic mantle domains. A sample from a continental lithospheric mantle domain is also examined. All samples have identical Ru isotopic compositions, within analytical uncertainties, indicating that Ru isotopes are well mixed in the oceanic mantle, defining a μ100Ru value of 1.2 ± 7.2 (2SD). The only known meteorites with the same Ru isotopic composition are enstatite chondrites and, when corrected for the effects of cosmic ray exposure, members of the Main Group and sLL subgroup of the IAB iron meteorite complex which have a collective CRE corrected μ100Ru value of 0.9 ± 3.0. This suggests that materials from the region(s) of the solar nebula sampled by these meteorites likely contributed the dominant portion of late accreted materials to Earth's mantle.

The influence of diet on the δ 13C of shell carbon in the pulmonate snail Helix aspersa

NASA Astrophysics Data System (ADS)

Stott, Lowell D.

2002-02-01

The influence of diet and atmospheric CO 2 on the carbon isotope composition of shell aragonite and shell-bound organic carbon in the pulmonate snail Helix aspersa raised in the laboratory was investigated. Three separate groups of snails were raised on romaine lettuce (C3 plant, δ 13C=-25.8‰), corn (C4 plant, δ 13C=-10.5‰), and sour orange ( 12C-enriched C3 plant, δ 13C=-39.1‰). The isotopic composition of body tissues closely tracked the isotopic composition of the snail diet as demonstrated previously. However, the isotopic composition of the acid insoluble organic matrix extracted from the aragonite shells does not track diet in all groups. In snails that were fed corn the isotopic composition of the organic matrix was more negative than the body by as much as 5‰ whereas the matrix was approximately 1‰ heavier than the body tissues in snails fed a diet of C3 plant material. These results indicate that isotopic composition of the organic matrix carbon cannot be used as an isotopic substrate for paleodietary reconstructions without first determining the source of the carbon and any associated fractionations. The isotopic composition of the shell aragonite is offset from the body tissues by 12.3‰ in each of the culture groups. This offset was not influenced by the consumption of carbonate and is not attributable to the diffusion of atmospheric CO 2 into the hemolymph. The carbon isotopic composition of shell aragonite is best explained in terms of equilibrium fractionations associated with exchange between metabolic CO 2 and HCO 3 in the hemolymph and the fractionation associated with carbonate precipitation. These results differ from previous studies, based primarily on samples collected in the field, that have suggested atmospheric carbon dioxide contributes significantly to the shell δ 13C. The culture results indicate that the δ 13C of aragonite is a good recorder of the isotopic composition of the snail body tissue, and therefore a better recorder of diet than is the insoluble shell organic carbon. Because the systematic fractionation of carbon isotopes within the snail is temperature dependent, the δ 13C of the shell could provide an independent technique for estimating paleotemperature changes.

Strontium and neodymium isotopes in hot springs on the East Pacific Rise and Guaymas Basin

NASA Technical Reports Server (NTRS)

Piepgras, D. J.; Wasserburg, G. J.

1985-01-01

Solutions collected from 21 deg N, East Pacific Rise (Epr) and Guaymas Basin, Gulf of California, are analyzed for Nd isotopic composition and Sm and Nd concentrations. The results indicate extensive but not complete isotopic exchange with Sr in the depleted oceanic crust and that Sr concentrations in these solutions are buffered. In contrast, the Nd data exhibit a wide range in isotopic composition and concentration between vents. Many samples show substantial contributions from MORB, but all have isotopic compositions below MORB, in spite of enrichments in Nd up to 100 times seawater. It is shown that the fluids must exchange Nd with a sedimentary reservoir having an isotopic composition less than Pacific seawater. Low-temperature reactions with metalliferous sediments on the flanks of the EPR may provide such a source. Using a simple box method, estimates of the hydrothermal fluxes of Nd are compared to fluxes which are necessary to maintain a radiogenic isotopic composition of about -3 in the Pacific against the influx of Antarctic waters. It is concluded that erosion from island arcs is the main source of radiogenic Nd in the Pacific.

Measurement of natural carbon isotopic composition of acetone in human urine.

PubMed

Yamada, Keita; Ohishi, Kazuki; Gilbert, Alexis; Akasaka, Mai; Yoshida, Naohiro; Yoshimura, Ryoko

2016-02-01

The natural carbon isotopic composition of acetone in urine was measured in healthy subjects using gas chromatography-combustion-isotope ratio mass spectrometry combined with headspace solid-phase microextraction (HS-SPME-GC-C-IRMS). Before applying the technique to a urine sample, we optimized the measurement conditions of HS-SPME-GC-C-IRMS using aqueous solutions of commercial acetone reagents. The optimization enabled us to determine the carbon isotopic compositions within ±0.2 ‰ of precision and ±0.3‰ of error using 0.05 or 0.2 mL of aqueous solutions with acetone concentrations of 0.3-121 mg/L. For several days, we monitored the carbon isotopic compositions and concentrations of acetone in urine from three subjects who lived a daily life with no restrictions. We also monitored one subject for 3 days including a fasting period of 24 h. These results suggest that changes in the availability of glucose in the liver are reflected in changes in the carbon isotopic compositions of urine acetone. Results demonstrate that carbon isotopic measurement of metabolites in human biological samples at natural abundance levels has great potential as a tool for detecting metabolic changes caused by changes in physiological states and disease.

Fabrication of in-situ grown graphene reinforced Cu matrix composites

NASA Astrophysics Data System (ADS)

Chen, Yakun; Zhang, Xiang; Liu, Enzuo; He, Chunnian; Shi, Chunsheng; Li, Jiajun; Nash, Philip; Zhao, Naiqin

2016-01-01

Graphene/Cu composites were fabricated through a graphene in-situ grown approach, which involved ball-milling of Cu powders with PMMA as solid carbon source, in-situ growth of graphene on flaky Cu powders and vacuum hot-press sintering. SEM and TEM characterization results indicated that graphene in-situ grown on Cu powders guaranteed a homogeneous dispersion and a good combination between graphene and Cu matrix, as well as the intact structure of graphene, which was beneficial to its strengthening effect. The yield strength of 244 MPa and tensile strength of 274 MPa were achieved in the composite with 0.95 wt.% graphene, which were separately 177% and 27.4% enhancement over pure Cu. Strengthening effect of in-situ grown graphene in the matrix was contributed to load transfer and dislocation strengthening.

Composite CuFe1 - xSnxO2/p-type silicon photodiodes

NASA Astrophysics Data System (ADS)

Al-Sehemi, Abdullah G.; Mensah-Darkwa, K.; Al-Ghamdi, Ahmed A.; Soylu, M.; Gupta, R. K.; Yakuphanoglu, F.

2017-06-01

CuFe1 - xSnxO2 composite thin film/p-type silicon diodes were prepared on substrate by sol-gel method (x = 0.00, 0.01, 0.03, 0.05, 0.07). The structure of CuFe1 - xSnxO2 composite thin films was studied using XRD analysis and films exhibited amorphous behavior. The elemental compositions and surface morphology of the films were characterized using SEM and EDX. EDX results confirmed the presence of the compositional elements. The optical band gap of CuFe1 - xSnxO2 composite thin films was determined using the optic spectra. The optical band gaps of the CuFe1 - xSnxO2 composite thin films were calculated using optical data and were found to be 3.75, 3.78, 3.80, 3.85 and 3.83 eV for x = 0.00, 0.01, 0.03, 0.05 and 0.07, respectively. The photoresponse and electrical properties of the Al/CuFe1 - xSnxO2/p-Si/Al diode were studied. The barrier height and ideality factor were determined to be averagely 0.67 eV and 2.6, respectively. The electrical and photoresponse characteristics of the diodes have been investigated under dark and solar light illuminations, respectively. The interface states were used to explain the results obtained in present study. CuFe1 - xSnxO2 photodiodes exhibited a high photoresponsivity to be used in optoelectronic applications.

Sr isotopic tracer study of the Samail ophiolite, Oman.

USGS Publications Warehouse

Lanphere, M.A.; Coleman, R.G.; Hopson, C.A.

1981-01-01

Rb and Sr concentrations and Sr-isotopic compositions were measured in 41 whole-rock samples and 12 mineral separates from units of the Samail ophiolite, including peridotite, gabbro, plagiogranite, diabase dykes, and gabbro and websterite dykes within the metamorphic peridotite. Ten samples of cumulate gabbro from the Wadir Kadir section and nine samples from the Wadi Khafifah section have 87Sr/86Sr ratios of 0.70314 + or - 0.00030 and 0.70306 + or - 0.00034, respectively. The dispersion in Sr- isotopic composition may reflect real heterogeneities in the magma source region. The average Sr-isotopic composition of cumulate gabbro falls in the range of isotopic compositions of modern MORB. The 87Sr/86Sr ratios of noncumulate gabbro, plagiogranite, and diabase dykes range 0.7034-0.7047, 0.7038-0.7046 and 0.7037- 0.7061, respectively. These higher 87Sr/86Sr ratios are due to alteration of initial magmatic compositions by hydrothermal exchange with sea-water. Mineral separates from dykes that cut harzburgite tectonite have Sr-isotopic compositions which agree with that of cumulate gabbro. These data indicate that the cumulate gabbro and the different dykes were derived from partial melting of source regions that had similar long-term histories and chemical compositions.-T.R.

Effect of titanium addition on the thermal properties of diamond/cu-ti composites fabricated by pressureless liquid-phase sintering technique.

PubMed

Chung, Chih-Yu; Chu, Chao-Hung; Lee, Mu-Tse; Lin, Chun-Ming; Lin, Su-Jien

2014-01-01

In this study, minor-addition elements such as Si, Co, Cr, W, Mo, and Ti were added to matrix to improve the wettability between the diamonds and Cu matrix. The pressureless liquid-phase sintering technique adopted in this study provides a low-cost method for producing diamond/Cu composites with high potential for industrial mass production. Thermal properties of the diamond/Cu-Ti composites fabricated by pressureless liquid-phase sintering at 1373 K with variation in Ti contents were thoroughly investigated. XRD and TEM analysis show that TiC layer formed in the interface between Cu and diamond. The composites exhibited thermal conductivity as high as 620 W/m · K for 50 vol% diamond/Cu-0.6 at % Ti composite with diamond particle size of 300 µm. This value comes up to 85% of the thermal conductivity calculated by the Hasselman and Johnson (H-J) theoretical analysis. Under these conditions, a suitable coefficient of thermal expansion of 6.9 ppm/K was obtained.

Effect of Titanium Addition on the Thermal Properties of Diamond/Cu-Ti Composites Fabricated by Pressureless Liquid-Phase Sintering Technique

PubMed Central

Chung, Chih-Yu; Chu, Chao-Hung; Lee, Mu-Tse; Lin, Chun-Ming; Lin, Su-Jien

2014-01-01

In this study, minor-addition elements such as Si, Co, Cr, W, Mo, and Ti were added to matrix to improve the wettability between the diamonds and Cu matrix. The pressureless liquid-phase sintering technique adopted in this study provides a low-cost method for producing diamond/Cu composites with high potential for industrial mass production. Thermal properties of the diamond/Cu-Ti composites fabricated by pressureless liquid-phase sintering at 1373 K with variation in Ti contents were thoroughly investigated. XRD and TEM analysis show that TiC layer formed in the interface between Cu and diamond. The composites exhibited thermal conductivity as high as 620 W/m·K for 50 vol% diamond/Cu-0.6  at % Ti composite with diamond particle size of 300 µm. This value comes up to 85% of the thermal conductivity calculated by the Hasselman and Johnson (H-J) theoretical analysis. Under these conditions, a suitable coefficient of thermal expansion of 6.9 ppm/K was obtained. PMID:24715816

The effect of stoichiometry on Cu-Zn ordering kinetics in Cu2ZnSnS4 thin films

NASA Astrophysics Data System (ADS)

Rudisch, Katharina; Davydova, Alexandra; Platzer-Björkman, Charlotte; Scragg, Jonathan

2018-04-01

Cu-Zn disorder in Cu2ZnSnS4 (CZTS) may be responsible for the large open circuit voltage deficit in CZTS based solar cells. In this study, it was investigated how composition-dependent defect complexes influence the order-disorder transition. A combinatorial CZTS thin film sample was produced with a cation composition gradient across the sample area. The graded sample was exposed to various temperature treatments and the degree of order was analyzed with resonant Raman spectroscopy for various compositions ranging from E- and A-type to B-, F-, and C-type CZTS. We observe that the composition has no influence on the critical temperature of the order-disorder transition, but strongly affects the activation energy. Reduced activation energy is achieved with compositions with Cu/Sn > 2 or Cu/Sn < 1.8 suggesting an acceleration of the cation ordering in the presence of vacancies or interstitials. This is rationalized with reference to the effect of point defects on exchange mechanisms. The implications for reducing disorder in CZTS thin films are discussed in light of the new findings.

Rare earth element transport in the western North Atlantic inferred from Nd isotopic observations

NASA Technical Reports Server (NTRS)

Piepgras, D. J.; Wasserburg, G. J.

1987-01-01

The relationship between the Nd isotopic composition in the Atlantic waters and the origin and circulation of the water masses was investigated. Samples were collected in the western North Atlantic between 7 and 54 deg N. The isotopic composition (Nd-143/Nd-144 ratios) showed extensive vertical structure at all locations. In regions where a thermocline was well-developed, large isotopic shifts were observed across the base of the thermocline, while regions without a thermocline were characterized by much more gradual shifts in isotopic composition with depth. The data reveal an excellent correlation between the Nd isotopic distribution in the western North Atlantic water column and the distribution of water masses identified from temperature and salinity measurements.

Sm-Nd in marine carbonates and phosphates - Implications for Nd isotopes in seawater and crustal ages

NASA Technical Reports Server (NTRS)

Shaw, H. F.; Wasserburg, G. J.

1985-01-01

The possibility of establishing a record of variations in the isotopic composition of Nd in seawater over geologic time is explored. To construct such a record, a phase must be identified which incorporated Nd with the same isotopic composition as seawater at the time of its formation, preserves that composition, and which is relatively common in sediments. To evaluate the suitability of carbonates and phosphates, the Rb, Sr, Sm, and Nd concentrations and the Nd and Sr isotopic composition of a variety of modern and ancient marine calcite, aragonite, and apatite samples have been measured and the results are presented and discussed.

Fingerprints of carbon, nitrogen, and silicon isotopes in small interstellar SiC grains from the Murchison meteorite

NASA Technical Reports Server (NTRS)

Hoppe, Peter; Geiss, Johannes; Buehler, Fritz; Neuenschwander, Juerg; Amari, Sachiko; Lewis, Roy S.

1993-01-01

We report ion microprobe determinations of the carbon, nitrogen, and silicon isotopic compositions of small SiC grains from the Murchison CM2 chondrite. Analyses were made on samples containing variable numbers of grains and on 14 individual grains. In some cases the multiple-grain sample compositions were probably dominated by only one or two grains. Total ranges observed are given. Only a few grains show values near the range limits. Both the total ranges of carbon and nitrogen isotopic compositions, and even the narrower ranges typical for the majority of the grains, are similar to those observed for larger SiC grains. Two rare components appear to be present in the smaller-size fraction, one characterized by C-12/C-13 about 12-16 and the other by very heavy nitrogen. The carbon and nitrogen isotopic compositions qualitatively may reflect hydrostatic H-burning via the CNO cycle and He-burning in red giants, as well as explosive H-burning in novae. The silicon isotopic compositions of most grains qualitatively show what is the signature of He-burning. The silicon isotopic composition of one grain, however, suggests a different process.

Common Occurrence of Explosive Hydrogen Burning in Type II Supernovae

NASA Astrophysics Data System (ADS)

Liu, Nan; Stephan, Thomas; Boehnke, Patrick; Nittler, Larry R.; Meyer, Bradley S.; O’D. Alexander, Conel M.; Davis, Andrew M.; Trappitsch, Reto; Pellin, Michael J.

2018-03-01

We report Mo isotopic data for 16 15N-rich presolar SiC grains of type AB (14N/15N < solar, AB1) and their correlated Sr and Ba isotope ratios when available. Of the 16 AB1 grains, 8 show s-process Mo isotopic compositions, together with s-process Ba and/or Sr isotopic compositions. We found that a higher percentage of AB1 grains show anomalous isotopic compositions than that of AB2 grains (14N/15N > solar), thus providing further support to the division of the two AB subgroups recently proposed by Liu et al., who showed that AB1 grains most likely originated from Type II supernovae (SNe) with explosive H burning. Comparison of the Sr, Mo, and Ba isotopic compositions of the AB1 grains with SN model predictions indicates that the s-process isotopic compositions of AB1 grains resulted from neutron-capture processes occurring during the progenitor massive stars’ pre-SN evolution rather than from an explosive neutron-capture process. In addition, the observations of (1) explosive H burning occurring in the C-rich regions of the progenitor SNe of X grains as suggested by the isotopic compositions of X grains, and (2) explosive H burning occurring both at the bottom of the He/C zone and at the top of the He/N zone as suggested by model simulations, imply that explosive H burning is a common phenomenon in outer SN zones.

Common Occurrence of Explosive Hydrogen Burning in Type II Supernovae

DOE PAGES

Liu, Nan; Stephan, Thomas; Boehnke, Patrick; ...

2018-03-16

In this paper, we report Mo isotopic data for 16 15N-rich presolar SiC grains of type AB ( 14N/ 15N < solar, AB1) and their correlated Sr and Ba isotope ratios when available. Of the 16 AB1 grains, 8 show s-process Mo isotopic compositions, together with s-process Ba and/or Sr isotopic compositions. We found that a higher percentage of AB1 grains show anomalous isotopic compositions than that of AB2 grains ( 14N/ 15N > solar), thus providing further support to the division of the two AB subgroups recently proposed by Liu et al., who showed that AB1 grains most likelymore » originated from Type II supernovae (SNe) with explosive H burning. Comparison of the Sr, Mo, and Ba isotopic compositions of the AB1 grains with SN model predictions indicates that the s-process isotopic compositions of AB1 grains resulted from neutron-capture processes occurring during the progenitor massive stars' pre-SN evolution rather than from an explosive neutron-capture process. Finally, in addition, the observations of (1) explosive H burning occurring in the C-rich regions of the progenitor SNe of X grains as suggested by the isotopic compositions of X grains, and (2) explosive H burning occurring both at the bottom of the He/C zone and at the top of the He/N zone as suggested by model simulations, imply that explosive H burning is a common phenomenon in outer SN zones.« less

Common Occurrence of Explosive Hydrogen Burning in Type II Supernovae

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Nan; Stephan, Thomas; Boehnke, Patrick

In this paper, we report Mo isotopic data for 16 15N-rich presolar SiC grains of type AB ( 14N/ 15N < solar, AB1) and their correlated Sr and Ba isotope ratios when available. Of the 16 AB1 grains, 8 show s-process Mo isotopic compositions, together with s-process Ba and/or Sr isotopic compositions. We found that a higher percentage of AB1 grains show anomalous isotopic compositions than that of AB2 grains ( 14N/ 15N > solar), thus providing further support to the division of the two AB subgroups recently proposed by Liu et al., who showed that AB1 grains most likelymore » originated from Type II supernovae (SNe) with explosive H burning. Comparison of the Sr, Mo, and Ba isotopic compositions of the AB1 grains with SN model predictions indicates that the s-process isotopic compositions of AB1 grains resulted from neutron-capture processes occurring during the progenitor massive stars' pre-SN evolution rather than from an explosive neutron-capture process. Finally, in addition, the observations of (1) explosive H burning occurring in the C-rich regions of the progenitor SNe of X grains as suggested by the isotopic compositions of X grains, and (2) explosive H burning occurring both at the bottom of the He/C zone and at the top of the He/N zone as suggested by model simulations, imply that explosive H burning is a common phenomenon in outer SN zones.« less

Carbon, nitrogen, magnesium, silicon, and titanium isotopic compositions of single interstellar silicon carbide grains from the Murchison carbonaceous chondrite

NASA Technical Reports Server (NTRS)

Hoppe, Peter; Amari, Sachiko; Zinner, Ernst; Ireland, Trevor; Lewis, Roy S.

1994-01-01

Seven hundred and twenty SiC grains from the Murchison CM2 chondrite, ranging in size from 1 to 10 micrometers, were analyzed by ion microprobe mass spectrometry for their C-isotopic compositions. Subsets of the grains were also analyzed for N (450 grains), Si (183 grains), Mg (179 grains), and Ti (28 grains) isotopes. These results are compared with previous measurements on 41 larger SiC grains (up to 15 x 26 micrometers) from a different sample of Murchison analyzed by Virag et al. (1992) and Ireland, Zinner, & Amari (1991a). All grains of the present study are isotopically anomalous with C-12/C-13 ratios ranging from 0.022 to 28.4 x solar, N-14/N-15 ratios from 0.046 to 30 x solar, Si-29/Si-28 from 0.54 to 1.20 x solar, Si-30/Si-28 from 0.42 to 1.14 x solar, Ti-49/Ti-48 from 0.96 to 1.95 x solar, and Ti-50/Ti-48 from 0.94 to 1.39 x solar. Many grains have large Mg-26 excesses from the decay of Al-26 with inferred Al-26/Al-27 ratios ranging up to 0.61, or 12,200 x the ratio of 5 x 10(exp -5) inferred for the early solar system. Several groups can be distinguished among the SiC grains. Most of the grains have C-13 and N-14 excesses, and their Si isotopic compositions (mostly excesses in Si-29 and Si-30) plot close to a slope 1.34 line on a Delta Si-29/Si-28 versus Delta Si-30/Si-28 three-isotope plot. Grains with small C-12/C-13 ratios (less than 10) tend to have smaller or no N-14 excesses and high Al-26/Al-27 ratios (up to 0.01). Grains with C-12/C-13 greater than 150 fall into two groups: grains X have N-15 excesses and Si-29 and Si-30 deficits and the highest (0.1 to 0.6) Al-26/Al-27 ratios; grains Y have N-14 excesses and plot on a slope 0.35 line on a Si three-isotope plot. In addition, large SiC grains of the Virag et al. (1992) study fall into three-distinct clusters according to their C-, Si-, and Ti-isotopic compositions. The isotopic diversity of the grains and the clustering of their isotopic compositions imply distinct and multiple stellar sources. The C- and N-isotopic compositions of most grains are consistent with H-burning in the CNO cycle. These and s-process Kr, Xe, Ba, and Nd suggest asymptotic giant branch (AGB) or Wolf-Rayet stars as likely sources for the grains, but existing models of nucleosynthesis in these stellar sites fail to account in detail for all the observed isotopic compositions. Special problems are posed by grains with C-12/C-13 less than 10 and almost normal and heavy N-isotopic compositions. Also the Si- and Ti-isotopic compositions, with excesses in Si-29 and Si-30 relative to Si-28 and excesses in all Ti isotopes relative to Ti-48, do not precisely conform with the compositions predicted for slow neutron capture. Additional theoretical efforts are needed to achieve an understanding of the isotopic composition of the SiC grains and their stellar sources.

Rb-Sr and Sm-Nd Ages of Zagami DML and SR Isotopic Heterogeneity in Zagami

NASA Technical Reports Server (NTRS)

Nyquist, L.aurenceE.; Shih, C.-Y.; Reese, Y. D.

2010-01-01

Zagami contains lithologic heterogeneity suggesting that it did not form in a homogeneous, thick lava flow [1]. We have previously investigated the Sr and Nd isotopic systematics of Coarse-Grained (CG) and Fine-Grained (FG) lithologies described by [2]. Both appear to belong to Normal Zagami (NZ) [1,3], but their initial Sr-isotopic compositions differ [4,5]. Here we report new analyses of the Dark Mottled Lithology (DML, [3]) that show its age and initial Sr and Nd isotopic compositions to be identical within error limits with those of CG, but Sr initial isotopic compositions differ from those of FG.

Mesozoic Magmatism and Base-Metal Mineralization in the Fortymile Mining District, Eastern Alaska - Initial Results of Petrographic, Geochemical, and Isotopic Studies in the Mount Veta Area

USGS Publications Warehouse

Dusel-Bacon, Cynthia; Slack, John F.; Aleinikoff, John N.; Mortensen, James K.

2009-01-01

We present here the initial results of a petrographic, geochemical, and isotopic study of Mesozoic intrusive rocks and spatially associated Zn-Pb-Ag-Cu-Au prospects in the Fortymile mining district in the southern Eagle quadrangle, Alaska. Analyzed samples include mineralized and unmineralized drill core from 2006 and 2007 exploration by Full Metal Minerals, USA, Inc., at the Little Whiteman (LWM) and Fish prospects, and other mineralized and plutonic samples collected within the mining district is part of the USGS study. Three new ion microprobe U-Pb zircon ages are: 210 +- 3 Ma for quartz diorite from LWM, 187 +- 3 Ma for quartz monzonite from Fish, and 70.5 +- 1.1 Ma for altered rhyolite porphyry from Fish. We also present 11 published and unpublished Mesozoic thermal ionization mass spectrometric U-Pb zircon and titanite ages and whole-rock geochemical data for the Mesozoic plutonic rocks. Late Triassic and Early Jurassic plutons generally have intermediate compositions and are slightly foliated, consistent with synkinematic intrusion. Several Early Jurassic plutons contain magmatic epidote, indicating emplacement of the host plutons at mesozonal crustal depths of greater than 15 km. Trace-element geochemical data indicate an arc origin for the granitoids, with an increase in the crustal component with time. Preliminary study of drill core from the LWM Zn-Pb-Cu-Ag prospect supports a carbonate-replacement model of mineralization. LWM massive sulfides consist of sphalerite, galena, and minor pyrite and chalcopyrite, in a gangue of calcite and lesser quartz; silver resides in Sb-As-Ag sulfosalts and pyrargyrite, and probably in submicroscopic inclusions within galena. Whole-rock analyses of LWM drill cores also show elevated In, an important metal in high-technology products. Hypogene mineralized rocks at Fish, below the secondary Zn-rich zone, are associated with a carbonate host and also may be of replacement origin, or alternatively, may be a magnetite-bearing Zn skarn. Cu-Zn-Pb-Ag-Au showings at the Oscar pros-pect occur in marble-hosted magnetite and pyrrhotite skarn that is spatially related to the stocks, dikes, and sills of the Early Jurassic syenite of Mount Veta. Mineralized rocks at the Eva Creek Ag-Zn-Pb-Cu prospect are within 1.5 km of the Mount Veta pluton, which is epidotized and locally altered along its contact with metamorphosed country rock east of the prospect. We report five new sulfide Pb-isotopic analyses from the LWM, Oscar, and Eva Creek prospects and compare these sulfide Pb-isotopic ratios with those for sulfides from nearby deposits and prospects in the Yukon-Tanana Upland and with feldspar Pb-isotopic ratios for Mesozoic plutons in the region. Disparities between the Pb-isotopic ratios for sulfides and igneous feldspars are consistent with a carbonate-replacement model for both the LWM and Eva Creek prospects. The presence in the Fortymile district of base-metal sulfides within both calc-silicate-rich skarns and the calc-silicate-free carbonate replacement deposits may reflect multistage mineralization by magmatic-hydrothermal systems during the emplacement of two or more magmatically unrelated igneous intrusions. Alternatively, all of the mineralized occurrences could be products of one regionally zoned system that formed during the intrusion of a single pluton. In addition to the likely origin of some of the base-metal occurrences by intrusion-related hydrothermal fluids, proximity of the LWM prospect to the northeast-striking, high-angle Kechumstuk Fault suggests that fluid flow along the fault also played an important role during carbonate-replacement mineralization.

Evidence for a sulfur-undersaturated lunar interior from the solubility of sulfur in lunar melts and sulfide-silicate partitioning of siderophile elements

NASA Astrophysics Data System (ADS)

Steenstra, E. S.; Seegers, A. X.; Eising, J.; Tomassen, B. G. J.; Webers, F. P. F.; Berndt, J.; Klemme, S.; Matveev, S.; van Westrenen, W.

2018-06-01

Sulfur concentrations at sulfide saturation (SCSS) were determined for a range of low- to high-Ti lunar melt compositions (synthetic equivalents of Apollo 14 black and yellow glass, Apollo 15 green glass, Apollo 17 orange glass and a late-stage lunar magma ocean melt, containing between 0.2 and 25 wt.% TiO2) as a function of pressure (1-2.5 GPa) and temperature (1683-1883 K). For the same experiments, sulfide-silicate partition coefficients were derived for elements V, Cr, Mn, Co, Cu, Zn, Ga, Ge, As, Se, Mo, Sn, Sb, Te, W and Pb. The SCSS is a strong function of silicate melt composition, most notably FeO content. An increase in temperature increases the SCSS and an increase in pressure decreases the SCSS, both in agreement with previous work on terrestrial, lunar and martian compositions. Previously reported SCSS values for high-FeO melts were combined with the experimental data reported here to obtain a new predictive equation to calculate the SCSS for high-FeO lunar melt compositions. Calculated SCSS values, combined with previously estimated S contents of lunar low-Ti basalts and primitive pyroclastic glasses, suggest their source regions were not sulfide saturated. Even when correcting for the currently inferred maximum extent of S degassing during or after eruption, sample S abundances are still > 700 ppm lower than the calculated SCSS values for these compositions. To achieve sulfide saturation in the source regions of low-Ti basalts and lunar pyroclastic glasses, the extent of degassing of S in lunar magma would have to be orders of magnitude higher than currently thought, inconsistent with S isotopic and core-to-rim S diffusion profile data. The only lunar samples that could have experienced sulfide saturation are some of the more evolved A17 high-Ti basalts, if sulfides are Ni- and/or Cu rich. Sulfide saturation in the source regions of lunar melts is also inconsistent with the sulfide-silicate partitioning systematics of Ni, Co and Cu. Segregation of significant quantities of (non)-stoichiometric sulfides during fractional crystallization would result in far larger depletions of Ni, Co and Cu than observed, whereas trends in their abundances are more likely explained by olivine fractionation. The sulfide exhaustion of the lunar magma source regions agrees with previously proposed low S abundances in the lunar core and mantle, and by extension with relatively minor degassing of S during the Moon-forming event. Our results support the hypothesis that refractory chalcophile and highly siderophile element systematics of low-Ti basalts and pyroclastic glasses reflect the geochemical characteristics of their source regions, instead of indicating the presence of residual sulfides in the lunar interior.

Structural and elemental characterization of high efficiency Cu2ZnSnS4 solar cells

NASA Astrophysics Data System (ADS)

Wang, Kejia; Shin, Byungha; Reuter, Kathleen B.; Todorov, Teodor; Mitzi, David B.; Guha, Supratik

2011-01-01

We have carried out detailed microstructural studies of phase separation and grain boundary composition in Cu2ZnSnS4 based solar cells. The absorber layer was fabricated by thermal evaporation followed by post high temperature annealing on hot plate. We show that inter-reactions between the bottom molybdenum and the Cu2ZnSnS4, besides triggering the formation of interfacial MoSx, results in the out-diffusion of Cu from the Cu2ZnSnS4 layer. Phase separation of Cu2ZnSnS4 into ZnS and a Cu-Sn-S compound is observed at the molybdenum-Cu2ZnSnS4 interface, perhaps as a result of the compositional out-diffusion. Additionally, grain boundaries within the thermally evaporated absorber layer are found to be either Cu-rich or at the expected bulk composition. Such interfacial compound formation and grain boundary chemistry likely contributes to the lower than expected open circuit voltages observed for the Cu2ZnSnS4 devices.

One-pot, self-assembled hydrothermal synthesis of 3D flower-like CuS/g-C3N4 composite with enhanced photocatalytic activity under visible-light irradiation

NASA Astrophysics Data System (ADS)

Khan, Azam; Alam, Umair; Raza, Waseem; Bahnemann, D.; Muneer, M.

2018-04-01

Novel visible-light-driven 3D flower-like CuS/g-C3N4 composites have been synthesized by different wt% of CuS using hydrothermal method and characterized by standard analytical techniques such as XRD, FTIR, XPS, BET, UV-Vis DRS spectroscopy, SEM-EDS, and TEM. SEM and TEM analyses showed an intimate interfacial contact between flower-like CuS and g-C3N4 sheet. The synthesized composite materials (CuS/g-C3N4) showed excellent photocatalytic activity for the decolorization of methylene blue (MB) in aqueous suspension under visible-light irradiation, compared with pure CuS and g-C3N4. Among various composites of CuS/g-C3N4, 10 wt% of CuS showed highest photocatalytic activity for the decolorization of dye (MB). This remarkably improved photocatalytic performance of the synthesized materials could be attributed to the synergistic interaction between CuS and g-C3N4, leading to prolonged lifetime of photo-generated e- and h+ pair through the Z-scheme system. A probable Z-scheme mechanism explaining the origin of enhanced performance of the composite material has been proposed. This work not only provides a facile way to synthesize 3D flower-like heterostructure, but also renders rational design for the development of highly efficient Z-scheme photocatalytic systems.

Au-HKUST-1 Composite Nanocapsules: Synthesis with a Coordination Replication Strategy and Catalysis on CO Oxidation.

PubMed

Liu, Yongxin; Zhang, Jiali; Song, Lingxiao; Xu, Wenyuan; Guo, Zanru; Yang, Xiaomin; Wu, Xiaoxin; Chen, Xi

2016-09-07

A novel coordination replication of Cu2O redox-template strategy is reported to efficiently fabricate Au-HKUST-1 composite nanocapsule, with a HKUST-1 sandwich shell and an embedded Au nanoparticles layer. The novel synthesis procedure involves forming Au nanoparticles on the surface of Cu2O, transforming partial Cu2O into HKUST-1 shell via coordination replication, and removing the residual Cu2O by acid. The as-prepared Au-HKUST-1 composite nanocapsules displayed high catalytic activity on CO oxidation.

Free Energy Defect Model for the Cu-In-Ga-Se Tetrahedral Lattice

NASA Astrophysics Data System (ADS)

Stanbery, B. J.

2003-03-01

The most efficient thin-film photovoltaic converters of solar insolation to electrical power have recently achieved conversion efficiencies exceeding 19%, and are based on light absorbing layers containing the binary alloy (CuInSe_2)_1-X(CuGaSe_2)X of the α phases of these ternary chalcopyrite compounds. A statistical quantum mechanical model of the thermodynamic equilibrium defect structure of the tetrahedral lattice of copper, indium, and selenium with composition in the domain between that of the stoichiometric CuIn_1-XGa_XSe2 alloy and the β phase Cu(In_1-XGa_X)_3Se5 composition is presented. Compositions more copper-deficient than the latter have been reported experimentally to result in a breakdown of the tetrahedral coordination characteristic of the chalcopyrite lattice. These computations are based on a cluster expansion algorithm that minimizes the total free energy of the system using the Gibbs-Duhem equation to compute quasichemical reaction equilibria between the neutral clusters, and explicitly incorporates Fermi-Dirac statistics to determine their ionization equilibria and consequent carrier concentrations in the conduction and valence bands. The results are consistent with recent experimental evidence that the stoichiometric CuIn_1-XGa_XSe2 composition segregates in equilibrium into a two-phase mixture of a copper-deficient quaternary Cu_1-γIn_1-XGa_XSe2 composition and the binary Cu_2-δSe compound. The model predicts that the hole majority carrier (p-type) can only be achieved in the equilibrium single-phase chalcopyrite lattice with compositions that correspond to Cu_1-γIn_1-XGa_XSe_2+ɛ with γ and ɛ >0. This predicted requirement for selenium enrichment compared to the stoichiometric CuIn_1-XGa_XSe2 alloy composition for the dominance of holes over electrons as the majority carrier type is consistent with experimental evidence, and is explained in terms of a transition of the dominant lattice defect from the selenium vacancy in the stoichiometric case to the copper vacancy defect in the selenium-enriched lattice. This result is of particular importance since all CuIn_1-XGa_XSe2 thin-film solar cells utilize p-type absorber films.

Behaviour of Structural Carbonate Stable Carbon and Oxygen Isotope Compositions in Bioapatite During Burning of Bone

NASA Astrophysics Data System (ADS)

Munro, L. E.; Longstaffe, F. J.; White, C. D.

2003-12-01

Bioapatite, the principal inorganic phase comprising bone, commonly contains a small fraction of carbonate, which has been substituted into the phosphate structure during bone formation. The isotopic compositions of both the phosphate oxygen and the structural carbonate oxygen are now commonly used in palaeoclimatological and bioarchaeological investigations. The potential for post-mortem alteration of these isotopic compositions, therefore, is of interest, with the behaviour of structural carbonate being of most concern. In bioarchaeological studies, alteration of bone isotopic compositions has the potential to occur not only during low-temperature processes associated with burial but also during food preparation involving heating (burning, boiling). Here, we examine the stable isotopic behaviour of structural carbonate oxygen and carbon, and coexisting phosphate oxygen during the burning of bone. Freshly deceased (6<8 months) white-tailed deer leg bones (Odocoileus virginianus) were collected from Pinery Provincial Park, Ontario, Canada. Each long bone was sectioned and incrementally heated from 25 to 900° C, in 25° intervals. The samples were then ground to a standardized grain-size (45<63μ m), and changes in bioapatite crystallinity (CI) were determined using powder X-ray diffraction (pXRD), and Fourier transform infra-red spectroscopy (FTIR). Combined differential thermal and thermogravimetric analyses (DTA/TG) were used to evaluate weight loss and associated reactions during heating. Stable carbon isotope compositions of the bioapatite remain relatively constant (+/-1‰ ) during heating to 650° C. A 4‰ increase in stable carbon isotopic composition then occurs between 650-750° C, accompanied by an increase in CI, followed by a 10‰ decline at temperatures above 800° C, as carbonate carbon is lost. Carbonate and phosphate oxygen isotopic compositions are correlated over the entire heating range, with carbonate being enriched relative to phosphate by about 8-10‰ below 500° C, 5-6‰ between 500-700° C, and 8-10‰ above 700° C. CI and oxygen isotopic compositions of carbonate and phosphate are not well correlated. Only modest CI changes are recorded from 25-675° C, compared with much larger changes in oxygen isotopic composition, especially above 300° C. On average, original isotopic compositions are largely preserved for both phosphate (+/-1‰ ) and carbonate (+/-2‰ ) oxygen at <300° C. At higher temperatures, however, both phosphate and carbonate oxygen in the bioapatite are systematically depleted of oxygen-18 relative to original values.

Solvothermal fabrication and enhanced visible light photocatalytic activity of Cu2O-reduced graphene oxide composite microspheres for photodegradation of Rhodamine B

NASA Astrophysics Data System (ADS)

Sun, Lingling; Wang, Guohong; Hao, Ruirui; Han, Deyan; Cao, Sheng

2015-12-01

The addition of graphene oxide (GO) in the semiconductors has been regarded as one of the effective methods to enhance their photocatalytic activity. In this study, Cu2O-reduced graphene oxide (Cu2O-rGO) composites with low loading (0-0.5 wt.%) of graphene oxide (GO) were produced by a one-step green solvothermal method in ethanol system by using Cu(NO3)2·3H2O and glutamic acid as copper precursor and reducing agent, respectively. During the solvothermal treatment, GO was reduced to rGO. The as-prepared Cu2O-reduced graphene oxide composite microspheres exhibited enhanced photocatalytic activity toward the degradation of RhB aqueous solution under visible light irradiation. At the optimal loading of graphene oxide (0.05 wt.%), Cu2O-rGO composites showed the highest photocatalytic activity, exceeding that of pure Cu2O and commercial Degussa P25 by a factor of 2.9 and 7.9, respectively. The enhanced photocatalytic activity may be ascribed to the strong coupling interaction between Cu2O particles and rGO nanosheets, which reduces the recombination of charge carriers.

Boron doping effect on the interface interaction and mechanical properties of graphene reinforced copper matrix composite

NASA Astrophysics Data System (ADS)

Fang, Bingcheng; Li, Jiajun; Zhao, Naiqin; Shi, Chunsheng; Ma, Liying; He, Chunnian; He, Fang; Liu, Enzuo

2017-12-01

In order to explore an efficient way of modifying graphene to improve the Cu/graphene interfacial bonding and remain the excellent mechanical and physical properties of graphene, the interaction between Cu and the pristine, atomic oxygen functionalized and boron- or nitrogen-doped graphene with and without defects was systematically investigated by density functional theory calculation. The electronic structure analysis revealed that the chemically active oxygen can enhance the binding energy Eb of Cu with graphene by forming strong covalent bonds, supporting the experimental study suggesting an vital role of intermediate oxygen in the improvement of the mechanical properties of graphene/Cu composites. Due to the strong hybridization between Cu-3d electron states and the 2p states of both boron and carbon atoms, the boron-doping effect is comparable to or even better than the chemical bridging role of oxygen in the reduced graphene oxide reinforced Cu matrix composite. Furthermore, we evidenced an enhancement of mechanical properties including bulk modulus, shear modulus and Young modulus of graphene/Cu composite after boron doping, which closely relates to the increased interfacial binding energy between boron-doped graphene and Cu surfaces.

Experimental Artifacts in Nitrogen Isotope Measurements of Meteorites

NASA Astrophysics Data System (ADS)

Kim, J. S.; Marti, K.

1993-07-01

Several research groups have studied contamination problems and molecular interferences in nitrogen isotope measurements, but some problems still require clarification. Protocols adopted for nitrogen isotope measurements generally consider questions such as CO interference, removal of hydrocarbons, and N2O and NO conversion [1]. In the analysis of nanogram amounts of N, contamination, exchange reactions, and interferences are more visible than in large N samples. During nitrogen measurements we observed several potential problems and developed an improved protocol to achieve high-quality isotopic data: 1. Nitrogen loss and isotopic exchange were observed on the extraction system wall. The wall has active surfaces produced by vapor deposition (previous samples) that absorb many molecules, including nitrogen. This absorbed nitrogen releases or exchanges nitrogen with sample N in the following extraction steps. Therefore the losses need to be calibrated and the extent of isotopic exchange determined at the nanogram level. A continuous adsorption during sample extraction of the gas phase onto zeolite at liquid nitrogen temperature reduces nitrogen loss and amount of exchange. 2. We also found nitrogen isotopic memory effect by CuO. During sample gas cleaning by CuO, nitrogen exchanges with residual nitrogen in the CuO, and losses to CuO by solubility and/or uptake of nitrogen during oxygen uptake. This effect is clearly visible after analysis of large amounts of nitrogen. In such cases the CuO blank showed traces of previously measured isotopic signatures. Therefore, the isotopic signature of the CuO blank must be assessed before proceeding. 3. NO interference was recognized. In measurements of N in bulk H chondrites, the steps above 900 degrees C show anomalous contribution to the mass 30 peak, which decreases rapidly with time in the mass spectrometer. Using the ratio mass 30 to mass 31 and the corresponding physical properties of the interfering compound, we identified the NO molecule. NO is produced during heating of the meteorites, and this molecule interacts with metal surfaces (e.g., valves and system metal). It is then released slowly from a metal surface and added to sample nitrogen during N transfer to the inlet volume of the mass spectrometer. Similar effects were reported last year [2], in addition to a rapid change of the measured 29/28 ratio. Hashizume and Sugiura concluded that curious phenomena indicate nonequilibria between two components, and thus the silicates in ordinary chondrites would not contain trapped nitrogen, which is in contradiction with their data. To eliminate the NO effect on mass 30, we made two modifications in the protocol. One is a final cleaning step of the gas phase using a glass finger at liquid nitrogen temperature; the other is the closing of the inlet valve after admitting the sample gas to the mass spectrometer. This protocol eliminates NO interference when the mass spectrometer is not contaminated by NO. 4. There are also nitrogen calibration issues. Last year nitrogen data for metal separates and bulk samples of some H chondrites were reported to reveal large isotopic variations (delta ^15N value from -44 to 119) [3]. Because Kung and Clayton [4] did not observe such variations, we measured nitrogen in Jilin (H5) and found a bulk average delta ^15N = 17 per mil. We also measured a metal separate from Forest Vale and observed a maximum value delta ^15N = 15 per mil. We were unable to confirm the value reported by [3]. We performed a series of calibrations against air nitrogen and NBS-steel standards to determine nitrogen loss and exchange, and against an internal meteorite standard (Cape York). Our analytical procedures are well reproduced. The NBS- steel and Cape York iron are therefore suitable as interlaboratory calibration standards for removal of experimental artifacts. References: [1] Boyd S. R. et al. (1988) J. Phys. E: Sci. Instrum., 21, 876- 885. [2] Hashizume K. and Sugiura N. (1992) GCA, 56, 1625-1631. [3] Hashizume K. and Sugiura N. (1992) Meteoritics, 27, 232. [4] Kung C. and Clayton R. N. (1978) EPSL, 38, 421-435.

Simultaneous adsorption of Cu2+ and Acid fuchsin (AF) from aqueous solutions by CMC/bentonite composite.

PubMed

Gong, Ning; Liu, Yanping; Huang, Ruihua

2018-04-21

Carboxymethyl-chitosan (CMC)/bentonite composite was prepared by the method of membrane-forming, and characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) techniques. The simultaneous adsorption of Cu 2+ and Acid fuchsin (AF) applying CMC/bentonite composite as an adsorbent in single or binary systems was investigated. The adsorption study was conducted systematically by varying the ratio of CMC to bentonite, adsorbent dosage, initial pH value, initial Cu 2+ (or AF) concentration, contact time and the interaction of two components in binary solutions. The results showed that the presence of Cu 2+ hindered the adsorption of AF, while the presence of AF almost had no influence on the adsorption of Cu 2+ in binary systems. The adsorption data of Cu 2+ and AF were both suitable for Langmuir isotherm model, and the maximum adsorption capacities of CMC/bentonite composite, according to the Langmuir isotherm model were 81.4 mg/g for Cu 2+ and 253.2 mg/g for AF at 298 K. The pseudo-second-order model could better describe the adsorption process of Cu 2+ and AF. Thermodynamic constant values illustrated that the adsorption of Cu 2+ was endothermic, while the adsorption process of AF was exothermic. Copyright © 2018. Published by Elsevier B.V.

Trace elements (Cu, Zn, and Hg) and δ13C/δ15N in seabird subfossils from three islands of the South China Sea and its implications.

PubMed

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.

Oxygen isotope analysis of fossil organic matter by secondary ion mass spectrometry

NASA Astrophysics Data System (ADS)

Tartèse, Romain; Chaussidon, Marc; Gurenko, Andrey; Delarue, Frédéric; Robert, François

2016-06-01

We have developed an analytical procedure for the measurement of oxygen isotope composition of fossil organic matter by secondary ion mass spectrometry (SIMS) at the sub-per mill level, with a spatial resolution of 20-30 μm. The oxygen isotope composition of coal and kerogen samples determined by SIMS are on average consistent with the bulk oxygen isotope compositions determined by temperature conversion elemental analysis - isotope ratio mass spectrometry (TC/EA-IRMS), but display large spreads of δ18O of ∼5-10‰, attributed to mixing of remnants of organic compounds with distinct δ18O signatures. Most of the δ18O values obtained on two kerogen residues extracted from the Eocene Clarno and Early Devonian Rhynie continental chert samples and on two immature coal samples range between ∼10‰ and ∼25‰. Based on the average δ18O values of these samples, and on the O isotope composition of water processed by plants that now constitute the Eocene Clarno kerogen, we estimated δ18Owater values ranging between around -11‰ and -1‰, which overall correspond well within the range of O isotope compositions for present-day continental waters. SIMS analyses of cyanobacteria-derived organic matter from the Silurian Zdanow chert sample yielded δ18O values in the range 12-20‰. Based on the O isotope composition measured on recent cyanobacteria from the hypersaline Lake Natron (Tanzania), and on the O isotope composition of the lake waters in which they lived, we propose that δ18O values of cyanobacteria remnants are enriched by about ∼18 ± 2‰ to 22 ± 2‰ relative to coeval waters. This relationship suggests that deep ocean waters in which the Zdanow cyanobacteria lived during Early Silurian times were characterised by δ18O values of around -5 ± 4‰. This study, establishing the feasibility of micro-analysis of Phanerozoic fossil organic matter samples by SIMS, opens the way for future investigations of kerogens preserved in Archean cherts and of the O isotopic composition of ocean water at that period in time.

Microstructure and Shear Strength in Brazing Joint of Mo-Cu Composite with 304 Stainless Steel by Ni-Cr-P Filler Metal

NASA Astrophysics Data System (ADS)

Wang, Juan; Wang, Jiteng; Li, Yajiang; Zheng, Deshuang

2015-07-01

The brazing of Mo-Cu composite and 304 stainless steel was carried out in vacuum with Ni-Cr-P filler metal at 980 °C for 20 min. Microstructure in Mo-Cu/304 stainless steel joint was investigated by field-emission scanning electron microscope (FE-SEM) with energy dispersive spectrometer (EDS) and shear strength was measured by shearing test. The results indicate that shear strength of the Mo-Cu/304 stainless steel joint is about 155 MPa. There forms eutectic structure of γ-Ni solid solution with Ni3P in the braze seam. Ni-Cu(Mo) and Ni-Fe solid solution are at the interface beside Mo-Cu composite and 304 stainless steel, respectively. Shear fracture exhibits mixed ductile-brittle fracture feature with trans-granular fracture, ductile dimples and tearing edges. Fracture originates from the interface between brazing seam and Mo-Cu composite and it propagates to the braze seam due to the formation of brittle Ni5P2 and Cr3P precipitation.

Copper Diffusion in Silicate Melts and Melt Inclusion Study on Volatiles in The Lunar Interior

NASA Astrophysics Data System (ADS)

Ni, Peng

This thesis focuses on the application of diffusion kinetics to both terrestrial and lunar geochemistry. In Chapters II and III, diffusivities of Cu in silicate melts were experimentally determined and used to discuss the role of Cu diffusion in formation of Cu ore deposits and also Cu isotope fractionation in tektites. In Chapters IV and V, lunar olivine-hosted melt inclusions are studied to understand their volatile loss during homogenization in lab, to estimate cooling rate for lunar Apollo sample 74220, and to estimate volatile abundance in the lunar mantle. Magmatic sulfide deposits and porphyry-type Cu deposits are two major types of Cu deposits that supply the world's Cu. In particular, porphyry-type Cu deposits provide ˜57% of the world's total discovered Cu. Recent studies suggest a potential role of diffusive transport of metals (e.g. Cu, Au, PGE, Mo) in the formation of magmatic sulfide deposits and porphyry-type deposits. Diffusivities of Cu in silicate melts, however, are poorly determined. In Chapters II and III of this thesis, Cu diffusion in basaltic melt and rhyolitic melts are studied by diffusion couple and chalcocite "dissolution" methods. Our results indicate high diffusivities of Cu and a general equation for Cu diffusion in silicate melts is obtained. The high diffusivity of Cu indicate that partition of Cu between the silicate phase and the sulfide or fluid phase can be assumed to be in equilibrium during the formation of magmatic sulfide deposits or porphyry-type deposits. In addition, our Cu diffusion data helps explain why Cu isotopes are more fractionated than Zn isotopes in tektites. Volatile abundances in the lunar mantle have profound implications for the origin of the Moon, which was thought to be bone-dry till about a decade ago, when trace amounts of H2O were detected in various types of lunar samples. In particular, high H2O concentrations comparable to mid-ocean ridge basalts were reported in lunar melt inclusions. There are still uncertainties, however, for lunar melt inclusion studies in at least two aspects. One is whether the low H2O/Ce ratios measured in homogenized crystalline inclusions are affected by the homogenization process. The other is that current estimation of volatile abundances in lunar mantle relies heavily on 74220, which is argued to be a local anomaly by some authors. In order to reach a conclusive answer on volatile abundances in lunar mantle, the above two questions have to be answered. To improve our understanding about these questions, in Chapter IV of this thesis, a series of experiments are carried out to understand possible volatile loss from lunar melt inclusions during homogenization. Our results indicate significant H2O loss from inclusions during homogenization in minutes, whereas loss of F, Cl or S is unlikely a concern under our experimental conditions. The most applicable way to preserve H2O during homogenization is to use large inclusions. In Chapter V of this thesis, volatile, trace and major element data for melt inclusions from 10020, 12040, 15016, 15647 and 74235 are reported. Our new data indicate large variation in H2O/Ce ratios from ˜77 to ˜1 across different lunar samples, which is at least partially due to H2O loss on lunar surface during cooling. In addition, evidences were found in F/Nd and S/Dy ratios that might suggest lunar mantle heterogeneity in terms of its volatile abundances.

Rainfall Type as a Dominant Control of the Isotopic Composition of Precipitation in the South Central United States

NASA Astrophysics Data System (ADS)

Sun, C.; Shanahan, T. M.; Partin, J. W.

2017-12-01

The processes that control the isotopic composition of precipitation in the mid-latitudes are understudied compared to the high and low latitudes, but are critical for interpreting paleo records using isotope proxies. To better understand these processes, we investigated changes of isotopic composition of rainwater in Central Texas using 20 months of event-based rainwater collection. We find that in both the event-based data and the monthly data from the Waco GNIP station, the dominant control on the isotopic composition of precipitation is the proportion that is derived from convective systems. This finding is consistent with previously reported data largely from tropical localities (Aggarwal et al., 2016), where large organized convective systems lead to high rainfall amounts and isotopically depleted precipitation. Although there are seasonal differences in the dominant rainfall types over the South Central US, with winter precipitation almost entirely stratiform, seasonality plays very little role in the net isotopic composition of precipitation because the total contribution during winter is small compared with spring, summer and fall. We also find that changes of source have little effect on the isotopic composition of rainfall, as the majority of the moisture is derived from the Gulf of Mexico with little influence of reevaporation or mixing. The majority of the warm season precipitation in the South Central US occurs in association with mesoscale convective systems (MCSs) and the development of these systems plays a critical role in the overall isotopic signature of precipitation. MCSs are characterized by a combination of intense, organized convection at their leading edges and trailing stratiform precipitation. Larger MCSs tend to contain higher proportions of stratiform rainfall and as a result, have isotopically depleted values. Proxy records from this region displaying more negative isotope values in the past should therefore be interpreted with caution as they could reflect either increases in cool versus warm season precipitation or changes in the intensity of warm season MCSs.

Silicon Isotopic Fractionation of CAI-like Vacuum Evaporation Residues

DOE Office of Scientific and Technical Information (OSTI.GOV)

Knight, K; Kita, N; Mendybaev, R

2009-06-18

Calcium-, aluminum-rich inclusions (CAIs) are often enriched in the heavy isotopes of magnesium and silicon relative to bulk solar system materials. It is likely that these isotopic enrichments resulted from evaporative mass loss of magnesium and silicon from early solar system condensates while they were molten during one or more high-temperature reheating events. Quantitative interpretation of these enrichments requires laboratory determinations of the evaporation kinetics and associated isotopic fractionation effects for these elements. The experimental data for the kinetics of evaporation of magnesium and silicon and the evaporative isotopic fractionation of magnesium is reasonably complete for Type B CAI liquidsmore » (Richter et al., 2002, 2007a). However, the isotopic fractionation factor for silicon evaporating from such liquids has not been as extensively studied. Here we report new ion microprobe silicon isotopic measurements of residual glass from partial evaporation of Type B CAI liquids into vacuum. The silicon isotopic fractionation is reported as a kinetic fractionation factor, {alpha}{sub Si}, corresponding to the ratio of the silicon isotopic composition of the evaporation flux to that of the residual silicate liquid. For CAI-like melts, we find that {alpha}{sub Si} = 0.98985 {+-} 0.00044 (2{sigma}) for {sup 29}Si/{sup 28}Si with no resolvable variation with temperature over the temperature range of the experiments, 1600-1900 C. This value is different from what has been reported for evaporation of liquid Mg{sub 2}SiO{sub 4} (Davis et al., 1990) and of a melt with CI chondritic proportions of the major elements (Wang et al., 2001). There appears to be some compositional control on {alpha}{sub Si}, whereas no compositional effects have been reported for {alpha}{sub Mg}. We use the values of {alpha}Si and {alpha}Mg, to calculate the chemical compositions of the unevaporated precursors of a number of isotopically fractionated CAIs from CV chondrites whose chemical compositions and magnesium and silicon isotopic compositions have been previously measured.« less

Metal-organic framework derived hollow polyhedron metal oxide posited graphene oxide for energy storage applications.

PubMed

Ramaraju, Bendi; Li, Cheng-Hung; Prakash, Sengodu; Chen, Chia-Chun

2016-01-18

A composite made from hollow polyhedron copper oxide and graphene oxide was synthesized by sintering a Cu-based metal-organic framework (Cu-MOF) embedded with exfoliated graphene oxide. As a proof-of-concept application, the obtained Cu(ox)-rGO materials were used in a lithium-ion battery and a sodium-ion battery as anode materials. Overall, the Cu(ox)-rGO composite delivers excellent electrochemical properties with stable cycling when compared to pure CuO-rGO and Cu-MOF.

Re-assessing the Molybdenum Isotope Composition of Pre-GOE Seawater: Evidence for Dynamic Ocean Redox

NASA Astrophysics Data System (ADS)

Ostrander, C. M.; Kendall, B.; Roy, M.; Romaniello, S. J.; Nunn, S. J.; Gordon, G. W.; Olson, S. L.; Lyons, T. W.; Zheng, W.; Anbar, A. D.

2016-12-01

Molybdenum (Mo) isotope compositions of Archean shales can provide important insights into ocean and atmosphere redox dynamics prior to the Great Oxidation Event (GOE). Unfortunately, the relatively limited Mo isotope database and small number of sample sets for Archean shales do not allow for in-depth reconstructions and specifically make it difficult to differentiate global from local effects. To accurately estimate the Mo isotope composition of Archean seawater and better investigate the systematics of local and global redox, more complete sample sets are needed. We carried out a Mo isotope analysis of the euxinic 2.65 Ga Roy Hill Shale sampled in two stratigraphically correlated cores, and revisited the well-studied euxinic 2.5 Ga Mt. McRae Shale in higher resolution. Our data show contrasting Mo isotope values in the 2.65 Ga Roy Hill Shale between near- and offshore depositional environments, with systematically heavier isotope values in the near-shore environment. High-resolution analysis of the Mt. McRae Shale yields oscillating Mo concentrations and isotope values at the cm- to dm-scale during the well-characterized "whiff of O2" interval, with the heaviest isotope values measured during euxinic deposition. Variations in the measured isotope values within each section are primarily associated with redox changes in the local depositional environment and amount of detrital content. Both non-quantitative removal of Mo associated with incorporation into non-euxinic sediments and large detrital Mo contributions shift some measured isotopic compositions toward lighter values. This is readily apparent in the near-shore Roy Hill Shale section and the Mt. McRae Shale, but may not fully explain variations observed in the offshore Roy Hill Shale deposit. Here, euxinic deposition is not accompanied by Mo enrichments or isotopic compositions as heavy as the near-shore equivalent, even after detrital correction. This disparity between the near- and offshore environment could signify spatial variation in the Mo isotope composition of 2.65 Ga seawater and highlights the need for multi-site and high-resolution studies in order to best assess paleoenvironmental conditions.

Trace and minor element variations and sulfur isotopes in crystalline and colloform ZnS: Incorporation mechanisms and implications for their genesis

USGS Publications Warehouse

Pfaff, Katharina; Koenig, Alan; Wenzel, Thomas; Ridley, Ian; Hildebrandt, Ludwig H.; Leach, David L.; Markl, Gregor

2011-01-01

Various models have been proposed to explain the formation mechanism of colloform sphalerite, but the origin is still under debate. In order to decipher influences on trace element incorporation and sulfur isotope composition, crystalline and colloform sphalerite from the carbonate-hosted Mississippi-Valley Type (MVT) deposit near Wiesloch, SW Germany, were investigated and compared to sphalerite samples from 52 hydrothermal vein-type deposits in the Schwarzwald ore district, SW Germany to study the influence of different host rocks, formation mechanisms and fluid origin on trace element incorporation. Trace and minor element incorporation in sphalerite shows some correlation to their host rock and/or origin of fluid, gangue, paragenetic minerals and precipitation mechanisms (e.g., diagenetic processes, fluid cooling or fluid mixing). Furthermore, crystalline sphalerite is generally enriched in elements like Cd, Cu, Sb and Ag compared to colloform sphalerite that mainly incorporates elements like As, Pb and Tl. In addition, sulfur isotopes are characterized by positive values for crystalline and strongly negative values for colloform sphalerite. The combination of trace element contents, typical minerals associated with colloform sphalerite from Wiesloch, sulfur isotopes and thermodynamic considerations helped to evaluate the involvement of sulfate-reducing bacteria in water-filled karst cavities. Sulfate-reducing bacteria cause a sulfide-rich environment that leads in case of a metal-rich fluid supply to a sudden oversaturation of the fluid with respect to galena, sphalerite and pyrite. This, however, exactly coincides with the observed crystallization sequence of samples involving colloform sphalerite from the Wiesloch MVT deposit.

Origin and tectonic implications of the Zhaxikang Pb-Zn-Sb-Ag deposit in northern Himalaya: evidence from structures, Re-Os-Pb-S isotopes, and fluid inclusions

NASA Astrophysics Data System (ADS)

Zhou, Qing; Li, Wenchang; Qing, Chengshi; Lai, Yang; Li, Yingxu; Liao, Zhenwen; Wu, Jianyang; Wang, Shengwei; Dong, Lei; Tian, Enyuan

2018-04-01

The Zhaxikang Pb-Zn-Sb-Ag-(Au) deposits, located in the eastern part of northern Himalaya, totally contain more than 1.146 million tonnes (Mt) of Pb, 1.407 Mt of Zn, 0.345 Mt of Sb, and 3 kilotonnes (kt) of Ag. Our field observations suggest that these deposits are controlled by N-S trending and west- and steep-dipping normal faults, suggesting a hydrothermal rather than a syngenetic sedimentary origin. The Pb-Zn-Sb-Ag-(Cu-Au) mineralization formed in the Eocene as indicated by a Re-Os isochron age of 43.1 ± 2.5 Ma. Sulfide minerals have varying initial Pb isotopic compositions, with (206Pb/204Pb)i of 19.04-19.68, (207Pb/204Pb)i of 15.75-15.88, and (208Pb/204Pb)i of 39.66-40.31. Sulfur isotopic values display a narrow δ34S interval of +7.8-+12.2‰. These Pb-S isotopic data suggest that the Zhaxikang sources of Pb and S should be mainly from the coeval felsic magmas and partly from the surrounding Mesozoic strata including metasedimentary rocks and layered felsic volcanic rocks. Fluid inclusion studies indicate that the hydrothermal fluids have medium temperatures (200-336 °C) but varying salinities (1.40-18.25 wt.% NaCl equiv.) with densities of 0.75-0.95 g/cm3, possibly suggesting an evolution mixing between a high salinity fluid, perhaps of magmatic origin, with meteoric water.

The Impact of Invasive Earthworm Activity on Biopolymer Character of ýDecayed Litter ý

NASA Astrophysics Data System (ADS)

Filley, T.; Crow, S.; Johnston, C.; McCormick, M.; Szlavecz, K.

2007-12-01

Over the last 400-500 years invasive European earthworm populations have ýmoved steadily into North American forests either previously devoid of ýearthworms or that contained their own native populations. This has profound ýimpacts upon litter decay and soil organic matter dynamics. To determine the ýimpact of earthworm activity on the biopolymer and stable isotope chemistry of ýlitter residues and the nature of organic carbon moved to the soil profile we ýanalyzed tulip poplar leaves from a multi-year addition experiment in open ýsurface decay litter and litter bag decay experiments, as well as the associated ýsoils among forest plots that varied in non-native earthworm density and ýbiomass. The chemical alteration of biopolymers was tracked with FTIR ýspectroscopy, 13C-TMAH thermochemolysis, alkaline CuO extraction, and stable ýisotope mass spectrometry. Earthworm activity resulted in residues and soil ýparticulate organic matter depleted in cuticular aliphatic components and ýpolyphenols but highly enriched in ether-linked lignin with respect to initial litter ýmaterial. Decay in low earthworm abundance plots, as well as all experiments ýwith earthworm-excluding litter bags, resulted in enrichment in cutin aliphatics ýand only minor increases in ether linked lignin phenols which was also reflected ýin the soils below the amendments. Additionally, the stable carbon and nitrogen ýisotope composition of tulip poplar residues became isotopically distinct. The ýresults from litter bag decays were only reflective of the chemistry at sites with ývery low earthworm abundances. ý

Chemical characteristics, including stable-isotope ratios, of surface water and ground water from selected sources in and near East Fork Armells Creek basin, southeastern Montana, 1985

USGS Publications Warehouse

Ferreira, R.F.; Lambing, J.H.; Davis, R.E.

1989-01-01

Water samples were collected from 29 sites to provide synoptic chemical data, including stable-isotope ratios, for an area of active surface coal mining and to explore the effectiveness of using the data to chemically distinguish water from different aquifers. Surface-water samples were collected from one spring, four sites on East Armells Creek, one site on Stocker Creek, and two fly-ash ponds. Streamflows in East Fork Armells Creek ranged from no flow in several upstream reaches to 2.11 cu ft/sec downstream from Colstrip, Montana. Only one tributary, Stocker Creek, was observed to contribute surface flow in the study area. Groundwater samples were collected from wells completed in Quaternary alluvium or mine spoils, Rosebud overburden, Rosebud coal bed, McKay coal bed, and sub-McKay deposits of the Tongue River Member, Paleocene Fort Union Formation. Dissolved-solids concentrations, in mg/L, were 840 at the spring, 3,100 to 5,000 in the streams, 13,000 to 22,000 in the ash ponds, and 690 to 4 ,100 in the aquifers. With few exceptions, water from the sampled spring, streams, and wells had similar concentrations of major constituents and trace elements and similar stable-isotope ratios. Water from the fly-ash ponds had larger concentrations of dissolved solids, boron, and manganese and were isotopically more enriched in deuterium and oxygen-18 than water from other sources. Water from individual aquifers could not be distinguished by either ion-composition diagrams or statistical cluster analyses. (USGS)

Cryogenic Calcite: A Morphologic and Isotopic Analog to the ALH84001 Carbonates

NASA Technical Reports Server (NTRS)

Niles, P. B.; Leshin, L. A.; Socki, R. A.; Guan, Y.; Ming, D. W.; Gibson, E. K.

2004-01-01

Martian meteorite ALH84001 carbonates preserve large and variable microscale isotopic compositions, which in some way reflect their formation environment. These measurements show large variations (>20%) in the carbon and oxygen isotopic compositions of the carbonates on a 10-20 micron scale that are correlated with chemical composition. However, the utilization of these data sets for interpreting the formation conditions of the carbonates is complex due to lack of suitable terrestrial analogs and the difficulty of modeling under non-equilibrium conditions. Thus, the mechanisms and processes are largely unknown that create and preserve large microscale isotopic variations in carbonate minerals. Experimental tests of the possible environments and mechanisms that lead to large microscale isotopic variations can help address these concerns. One possible mechanism for creating large carbon isotopic variations in carbonates involves the freezing of water. Carbonates precipitate during extensive CO2 degassing that occurs during the freezing process as the fluid s decreasing volume drives CO2 out. This rapid CO2 degassing results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing an enrichment of 13C in the remaining dissolved bicarbonate. This study seeks to determine the suitability of cryogenically formed carbonates as analogs to ALH84001 carbonates. Specifically, our objective is to determine how accurately models using equilibrium fractionation factors approximate the isotopic compositions of cryogenically precipitated carbonates. This includes determining the accuracy of applying equilibrium fractionation factors during a kinetic process, and determining how isotopic variations in the fluid are preserved in microscale variations in the precipitated carbonates.

The Reliability of Microalloyed Sn-Ag-Cu Solder Interconnections Under Cyclic Thermal and Mechanical Shock Loading

NASA Astrophysics Data System (ADS)

Mattila, Toni T.; Hokka, Jussi; Paulasto-Kröckel, Mervi

2014-11-01

In this study, the performance of three microalloyed Sn-Ag-Cu solder interconnection compositions (Sn-3.1Ag-0.52Cu, Sn-3.0Ag-0.52Cu-0.24Bi, and Sn-1.1Ag-0.52Cu-0.1Ni) was compared under mechanical shock loading (JESD22-B111 standard) and cyclic thermal loading (40 ± 125°C, 42 min cycle) conditions. In the drop tests, the component boards with the low-silver nickel-containing composition (Sn-Ag-Cu-Ni) showed the highest average number of drops-to-failure, while those with the bismuth-containing alloy (Sn-Ag-Cu-Bi) showed the lowest. Results of the thermal cycling tests showed that boards with Sn-Ag-Cu-Bi interconnections performed the best, while those with Sn-Ag-Cu-Ni performed the worst. Sn-Ag-Cu was placed in the middle in both tests. In this paper, we demonstrate that solder strength is an essential reliability factor and that higher strength can be beneficial for thermal cycling reliability but detrimental to drop reliability. We discuss these findings from the perspective of the microstructures and mechanical properties of the three solder interconnection compositions and, based on a comprehensive literature review, investigate how the differences in the solder compositions influence the mechanical properties of the interconnections and discuss how the differences are reflected in the failure mechanisms under both loading conditions.

Stable isotope study of a new chondrichthyan fauna (Kimmeridgian, Porrentruy, Swiss Jura): an unusual freshwater-influenced isotopic composition for the hybodont shark Asteracanthus

NASA Astrophysics Data System (ADS)

Leuzinger, L.; Kocsis, L.; Billon-Bruyat, J.-P.; Spezzaferri, S.; Vennemann, T.

2015-12-01

Chondrichthyan teeth (sharks, rays, and chimaeras) are mineralized in isotopic equilibrium with the surrounding water, and parameters such as water temperature and salinity can be inferred from the oxygen isotopic composition (δ18Op) of their bioapatite. We analysed a new chondrichthyan assemblage, as well as teeth from bony fish (Pycnodontiformes). All specimens are from Kimmeridgian coastal marine deposits of the Swiss Jura (vicinity of Porrentruy, Ajoie district, NW Switzerland). While the overall faunal composition and the isotopic composition of bony fish are generally consistent with marine conditions, unusually low δ18Op values were measured for the hybodont shark Asteracanthus. These values are also lower compared to previously published data from older European Jurassic localities. Additional analyses on material from Solothurn (Kimmeridgian, NW Switzerland) also have comparable, low-18O isotopic compositions for Asteracanthus. The data are hence interpreted to represent a so far unique, freshwater-influenced isotopic composition for this shark that is classically considered a marine genus. While reproduction in freshwater or brackish realms is established for other hybodonts, a similar behaviour for Asteracanthus is proposed here. Regular excursions into lower salinity waters can be linked to the age of the deposits and correspond to an ecological adaptation, most likely driven by the Kimmeridgian transgression and by the competition of the hybodont shark Asteracanthus with the rapidly diversifying neoselachians (modern sharks).

Stable isotope study of a new chondrichthyan fauna (Kimmeridgian, Porrentruy, Swiss Jura): an unusual freshwater-influenced isotopic composition for the hybodont shark Asteracanthus

NASA Astrophysics Data System (ADS)

Leuzinger, L.; Kocsis, L.; Billon-Bruyat, J.-P.; Spezzaferri, S.; Vennemann, T.

2015-08-01

Chondrichthyan teeth (sharks, rays and chimaeras) are mineralised in isotopic equilibrium with the surrounding water, and parameters such as water temperature and salinity can be inferred from the oxygen isotopic composition (δ18Op) of their bioapatite. We analysed a new chondrichthyan assemblage, as well as teeth from bony fish (Pycnodontiformes). All specimens are from Kimmeridgian coastal marine deposits of the Swiss Jura (vicinity of Porrentruy, Ajoie district, NW Switzerland). While the overall faunal composition and the isotopic composition of bony fish are consistent with marine conditions, unusually low δ18Op values were measured for the hybodont shark Asteracanthus. These values are also lower compared to previously published data from older European Jurassic localities. Additional analyses on material from Solothurn (Kimmeridgian, NW Switzerland) also have comparable, low-18O isotopic compositions for Asteracanthus. The data are hence interpreted to represent a so far unique, freshwater-influenced isotopic composition for this shark that is classically considered as a marine genus. While reproduction in freshwater or brackish realms is established for other hybodonts, a similar behaviour for Asteracanthus is proposed here. Regular excursions into lower salinity waters can be linked to the age of the deposits and correspond to an ecological adaptation, most likely driven by the Kimmeridgian transgression and by the competition of the primitive shark Asteracanthus with the rapidly diversifying neoselachians (modern sharks).

Microfluidic reactor synthesis and photocatalytic behavior of Cu@Cu2O nanocomposite

NASA Astrophysics Data System (ADS)

Xu, Lei; Srinivasakannan, C.; Peng, Jinhui; Yan, Mi; Zhang, Di; Zhang, Libo

2015-03-01

The Cu@Cu2O nanocomposites were synthesized by solution-phase synthesis of Cu nanoparticles in microfluidic reactor at room temperature, followed by controlling the oxidation process. The size, morphology, elemental compositions, and the chemical composition on the surface of Cu@Cu2O nanocomposite were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Experimental results demonstrated that the surface of the Cu nanoparticles was oxidized to Cu2O which serves as the shell of nanoparticle. The amount of Cu2O can be controlled by varying the drying temperature. Additionally the binary Cu@Cu2O nanocomposite along with H2O2 exhibited its potential as an excellent photocatalyst for degradation of methylene blue (MB) under UV irradiation.

The earliest Lunar Magma Ocean differentiation recorded in Fe isotopes

NASA Astrophysics Data System (ADS)

Wang, Kun; Jacobsen, Stein B.; Sedaghatpour, Fatemeh; Chen, Heng; Korotev, Randy L.

2015-11-01

Recent high-precision isotopic measurements show that the isotopic similarity of Earth and Moon is unique among all known planetary bodies in our Solar System. These observations provide fundamental constraints on the origin of Earth-Moon system, likely a catastrophic Giant Impact event. However, in contrast to the isotopic composition of many elements (e.g., O, Mg, Si, K, Ti, Cr, and W), the Fe isotopic compositions of all lunar samples are significantly different from those of the bulk silicate Earth. Such a global Fe isotopic difference between the Moon and Earth provides an important constraint on the lunar formation - such as the amount of Fe evaporation as a result of a Giant Impact origin of the Moon. Here, we show through high-precision Fe isotopic measurements of one of the oldest lunar rocks (4.51 ± 0.10 Gyr dunite 72 415), compared with Fe isotope results of other lunar samples from the Apollo program, and lunar meteorites, that the lunar dunite is enriched in light Fe isotopes, complementing the heavy Fe isotope enrichment in other lunar samples. Thus, the earliest olivine accumulation in the Lunar Magma Ocean may have been enriched in light Fe isotopes. This new observation allows the Fe isotopic composition of the bulk silicate Moon to be identical to that of the bulk silicate Earth, by balancing light Fe in the deep Moon with heavy Fe in the shallow Moon rather than the Moon having a heavier Fe isotope composition than Earth as a result of Giant Impact vaporization.

Isotope shift of the 590-cm-1 Raman feature in underdoped Bi2Sr2CaCu2O8+δ

NASA Astrophysics Data System (ADS)

Hewitt, K. C.; Wang, N. L.; Irwin, J. C.; Pooke, D. M.; Pantoja, A. E.; Trodahl, H. J.

1999-10-01

Raman-scattering studies have been performed on underdoped Bi2Sr2CaCu2O8+δ. In single crystals underdoped by oxygen removal, a 590-cm-1 peak is observed in the B1g spectrum. The feature is observed to soften in frequency by 3.8% with isotopic exchange of 16O by 18O. In contrast, the 590-cm-1 peak is not observed in crystals underdoped by Y substitution which suggests that it is a vibrational mode activated by oxygen deficency. We have also found that underdoping leads to a depletion of low-energy spectral weight from regions of the Fermi surface located near the Brillouin-zone axes.

The role of stable isotopes in understanding rainfall interception processes: a review

EPA Science Inventory

The isotopic composition of water transmitted by the canopy as throughfall or stemflow reflects important hydrologic processes occurring in the canopy. A synthesis of the literature shows that complex spatiotemporal variations of isotopic composition are created by canopy interce...

Biocomposites of copper-containing mesoporous bioactive glass and nanofibrillated cellulose: Biocompatibility and angiogenic promotion in chronic wound healing application.

PubMed

Wang, Xiaoju; Cheng, Fang; Liu, Jun; Smått, Jan-Henrik; Gepperth, David; Lastusaari, Mika; Xu, Chunlin; Hupa, Leena

2016-12-01

Biocomposites of copper-containing mesoporous bioactive glass (Cu-MBG) and nanofibrillated cellulose (NFC) were designated as potential dressing material for chronic wound healing. The phase composition and mesoporous micro-structure of the synthesized Cu-MBGs were elaborately characterized by combining several techniques, including TEM, SEM, XRD, SXAS and N 2 physisorption. High bioactivity of the Cu-MBG was confirmed in stimulated body fluids in vitro. A controlled dissolution of Cu from the glass suggests Cu-MBG a suitable source for Cu release in wound healing dressings. Depending on the content of Cu-MBG in the composite formulation, the composites were fabricated as membranes and aerogels. In biocompatibility assessment of the composites, a dose-dependent cytotoxicity of Cu 2+ on 3T3 fibroblasts was found. Importantly, a critical biological level of Cu 2+ below 10mg/L was suggested for the survival and growth of 3T3 fibroblasts. The Cu 2+ released from the composite aerogel of NFC and Cu-MBG showed a profound angiogenic effect in the 3D spheroid culture system of human umbilical vein endothelial cells. Moreover, the angiogenic gene expression of 3T3 fibroblast was upregulated in the real-time quantitative PCR analysis, which also confirms that the incorporation of Cu-MBG into NFC matrix enhances the proangiogenic potential of the biocomposites. In addition, composites of NFC and Cu-MBG also showed an inhibiting effect on the growth of E. coli. To address an urgent need in clinics on developing a new generation of therapeutic dressings with advanced functionalities, this study has exploited the utilization of Cu-containing mesoporous bioactive glass in the nanocellulose matrix to release Cu 2+ as therapeutic ions for its angiogenic effect on promoting wound healing. This manuscript reports research work on biomaterial design, fabrication development, material characterizations and bioassessments in 2D cellular studies. To utilize nanocellulose derived from the wood resource in biomedical applications is of great significance, due to its vast availability and bioeconomy competence. The use of Cu-containing bioactive glass in tissue engineering scaffolds, including wound healing, is an intriguing research topic, which has been recently discussed in the field of biomaterials. I think that our manuscript title with 'Biocomposites of copper-containing mesoporous bioactive glass and nanofibrillated cellulose: biocompatibility and angiogenic promotion in chronic wound healing application' will make its own contribution on understanding the complex effects of Cu 2+ on wound-healing-relevant events with acceptable novelty for Acta Biomaterialia. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Metal stable isotopes in weathering and hydrology: Chapter 10

USGS Publications Warehouse

Bullen, Thomas D.; Holland, Heinrich; Turekian, K.

2014-01-01

This chapter highlights some of the major developments in the understanding of the causes of metal stable isotope compositional variability in and isotope fractionation between natural materials and provides numerous examples of how that understanding is providing new insights into weathering and hydrology. At this stage, our knowledge of causes of stable isotope compositional variability among natural materials is greatest for the metals lithium, magnesium, calcium, and iron, the isotopes of which have already provided important information on weathering and hydrological processes. Stable isotope compositional variability for other metals such as strontium, copper, zinc, chromium, barium, molybdenum, mercury, cadmium, and nickel has been demonstrated but is only beginning to be applied to questions related to weathering and hydrology, and several research groups are currently exploring the potential. And then there are other metals such as titanium, vanadium, rhenium, and tungsten that have yet to be explored for variability of stable isotope composition in natural materials, but which may hold untold surprises in their utility. This impressive list of metals having either demonstrated or potential stable isotope signals that could be used to address important unsolved questions related to weathering and hydrology, constitutes a powerful toolbox that will be increasingly utilized in the coming decades.

Quality assurance and quality control in light stable isotope laboratories: A case study of Rio Grande, Texas, water samples

USGS Publications Warehouse

Coplen, T.B.; Qi, H.

2009-01-01

New isotope laboratories can achieve the goal of reporting the same isotopic composition within analytical uncertainty for the same material analysed decades apart by (1) writing their own acceptance testing procedures and putting them into their mass spectrometric or laser-based isotope-ratio equipment procurement contract, (2) requiring a manufacturer to demonstrate acceptable performance using all sample ports provided with the instrumentation, (3) for each medium to be analysed, prepare two local reference materials substantially different in isotopic composition to encompass the range in isotopic composition expected in the laboratory and calibrated them with isotopic reference materials available from the International Atomic Energy Agency (IAEA) or the US National Institute of Standards and Technology (NIST), (4) using the optimum storage containers (for water samples, sealing in glass ampoules that are sterilised after sealing is satisfactory), (5) interspersing among sample unknowns local laboratory isotopic reference materials daily (internationally distributed isotopic reference materials can be ordered at three-year intervals, and can be used for elemental analyser analyses and other analyses that consume less than 1 mg of material) - this process applies to H, C, N, O, and S isotope ratios, (6) calculating isotopic compositions of unknowns by normalising isotopic data to that of local reference materials, which have been calibrated to internationally distributed isotopic reference materials, (7) reporting results on scales normalised to internationally distributed isotopic reference materials (where they are available) and providing to sample submitters the isotopic compositions of internationally distributed isotopic reference materials of the same substance had they been analysed with unknowns, (8) providing an audit trail in the laboratory for analytical results - this trail commonly will be in electronic format and might include a laboratory information management system, (9) making at regular intervals a complete backup of laboratory analytical data (both of samples logged into the laboratory and of mass spectrometric analyses), being sure to store one copy of this backup offsite, and (10) participating in interlaboratory comparison exercises sponsored by the IAEA and other agencies at regular intervals. ?? Taylor & Francis.

Using Redwood Tree Ring Chronologies to Obtain the Long-View on California's Coastal Climate

NASA Astrophysics Data System (ADS)

Dawson, T. E.; Roden, J. S.; Voelker, S. L.; Johnstone, J. A.; Ambrose, A.

2014-12-01

Coast redwood (Sequoia sempervirens) occupies a long and narrow range at the land-sea interface from the southern Big Bur region to the California-Oregon boarder. Since mature trees can live in excess of 2000 years, using the interannual variability in the oxygen and carbon stable isotope composition of tree rings obtained from trees growing in different parts of the redwood range holds the potential for obtaining a long-term record of California's coastal climate, including the history of temperatures, low cloud / fog, rainfall and associated climatic drivers of their variation. We analyzed the oxygen and carbon stable isotope composition of tree ring cellulose from both tree cores and whole cross-sectional slabs and compared these data to several regional climate indicies and to published growth chronologies to obtain the long-view on California's coastal climate. Several highlights will be presented and discussed. These include: (1) redwoods faithfully record water sources they use in the oxygen stable isotope composition of their tree ring cellulose; (2) these is both strong watershed- and regional-scale coherence; (3) redwood tree ring carbon isotope composition shows its strongest correlations to tree water status, stand-scale humidity, and at the regional scale to what we term "summer precipitation" anomalies (lack of rain with presence of fog); also (4) that carbon stable isotope composition is very sensitive to within tree and stand microclimate while oxygen stable isotope composition seems to be sensitive to topographic site factors like slope position and proximity to riparian / gully habitats; (5) multivariate climatic analyses reveal that summertime drought recorded in the isotope excursions are most strongly linked to atmospheric circulation anomalies; and (6) that redwood tree rings and their isotope composition provide great potential for reconstructing high-resolution paleo-climate along the California coast.

Preparation and Enhanced Thermoelectric Performance of Cu2Se-SnSe Composite Materials

NASA Astrophysics Data System (ADS)

Peng, Zhi; He, Danqi; Mu, Xin; Zhou, Hongyu; Li, Cuncheng; Ma, Shifang; Ji, Pengxia; Hou, Weikang; Wei, Ping; Zhu, Wanting; Nie, Xiaolei; Zhao, Wenyu

2018-03-01

A series of p-type xCu2Se-SnSe (x = 0%, 0.10%, 0.15%, 0.20%, and 0.25%) composite thermoelectric materials have been prepared by the combination of ultrasonic dispersion and spark plasma sintering methods. The effects of secondary phase Cu2Se on the phase composition, microstructure, and thermoelectric properties of the composites were investigated. Microstructure characterization and elemental maps indicated Cu2Se grains uniformly distributed on the boundaries of the matrix. Transport measurements demonstrated that enhancement of the power factor and reduction of the thermal conductivity can be realized simultaneously by optimizing the adding content of Cu2Se. The highest ZT value of 0.51 at 773 K was achieved for the sample with x = 0.15%, increased by 24% compared with that of the SnSe matrix. These results demonstrate that optimizing the Cu2Se content can improve the thermoelectric performance of p-type SnSe polycrystalline materials.

Preparation and Enhanced Thermoelectric Performance of Cu2Se-SnSe Composite Materials

NASA Astrophysics Data System (ADS)

Peng, Zhi; He, Danqi; Mu, Xin; Zhou, Hongyu; Li, Cuncheng; Ma, Shifang; Ji, Pengxia; Hou, Weikang; Wei, Ping; Zhu, Wanting; Nie, Xiaolei; Zhao, Wenyu

2018-06-01

A series of p-type xCu2Se-SnSe ( x = 0%, 0.10%, 0.15%, 0.20%, and 0.25%) composite thermoelectric materials have been prepared by the combination of ultrasonic dispersion and spark plasma sintering methods. The effects of secondary phase Cu2Se on the phase composition, microstructure, and thermoelectric properties of the composites were investigated. Microstructure characterization and elemental maps indicated Cu2Se grains uniformly distributed on the boundaries of the matrix. Transport measurements demonstrated that enhancement of the power factor and reduction of the thermal conductivity can be realized simultaneously by optimizing the adding content of Cu2Se. The highest ZT value of 0.51 at 773 K was achieved for the sample with x = 0.15%, increased by 24% compared with that of the SnSe matrix. These results demonstrate that optimizing the Cu2Se content can improve the thermoelectric performance of p-type SnSe polycrystalline materials.

Titanium stable isotope investigation of magmatic processes on the Earth and Moon

NASA Astrophysics Data System (ADS)

Millet, Marc-Alban; Dauphas, Nicolas; Greber, Nicolas D.; Burton, Kevin W.; Dale, Chris W.; Debret, Baptiste; Macpherson, Colin G.; Nowell, Geoffrey M.; Williams, Helen M.

2016-09-01

We present titanium stable isotope measurements of terrestrial magmatic samples and lunar mare basalts with the aims of constraining the composition of the lunar and terrestrial mantles and evaluating the potential of Ti stable isotopes for understanding magmatic processes. Relative to the OL-Ti isotope standard, the δ49Ti values of terrestrial samples vary from -0.05 to +0.55‰, whereas those of lunar mare basalts vary from -0.01 to +0.03‰ (the precisions of the double spike Ti isotope measurements are ca. ±0.02‰ at 95% confidence). The Ti stable isotope compositions of differentiated terrestrial magmas define a well-defined positive correlation with SiO2 content, which appears to result from the fractional crystallisation of Ti-bearing oxides with an inferred isotope fractionation factor of ΔTi49oxide-melt = - 0.23 ‰ ×106 /T2. Primitive terrestrial basalts show no resolvable Ti isotope variations and display similar values to mantle-derived samples (peridotite and serpentinites), indicating that partial melting does not fractionate Ti stable isotopes and that the Earth's mantle has a homogeneous δ49Ti composition of +0.005 ± 0.005 (95% c.i., n = 29). Eclogites also display similar Ti stable isotope compositions, suggesting that Ti is immobile during dehydration of subducted oceanic lithosphere. Lunar basalts have variable δ49Ti values; low-Ti mare basalts have δ49Ti values similar to that of the bulk silicate Earth (BSE) while high-Ti lunar basalts display small enrichment in the heavy Ti isotopes. This is best interpreted in terms of source heterogeneity resulting from Ti stable isotope fractionation associated with ilmenite-melt equilibrium during the generation of the mantle source of high-Ti lunar mare basalts. The similarity in δ49Ti between terrestrial samples and low-Ti lunar basalts provides strong evidence that the Earth and Moon have identical stable Ti isotope compositions.

Derivation of S and Pb in phanerozoic intrusion-related metal deposits from neoproterozoic sedimentary pyrite, Great Basin, United States

USGS Publications Warehouse

Vikre, Peter G.; Poulson, S.R.; Koenig, Alan E.

2011-01-01

The thick (≤8 km), regionally extensive section of Neoproterozoic siliciclastic strata (terrigenous detrital succession, TDS) in the central and eastern Great Basin contains sedimentary pyrite characterized by mostly high δ34S values (−11.6 to 40.8‰, >70% exceed 10‰; 51 analyses) derived from reduction of seawater sulfate, and by markedly radiogenic Pb isotopes (207Pb/204Pb >19.2; 15 analyses) acquired from clastic detritus eroded from Precambrian cratonal rocks to the east-southeast. In the overlying Paleozoic section, Pb-Zn-Cu-Ag-Au deposits associated with Jurassic, Cretaceous, and Tertiary granitic intrusions (intrusion-related metal deposits) contain galena and other sulfide minerals with S and Pb isotope compositions similar to those of TDS sedimentary pyrite, consistent with derivation of deposit S and Pb from TDS pyrite. Minor element abundances in TDS pyrite (e.g., Pb, Zn, Cu, Ag, and Au) compared to sedimentary and hydrothermal pyrite elsewhere are not noticeably elevated, implying that enrichment in source minerals is not a precondition for intrusion-related metal deposits.Three mechanisms for transferring components of TDS sedimentary pyrite to intrusion-related metal deposits are qualitatively evaluated. One mechanism involves (1) decomposition of TDS pyrite in thermal aureoles of intruding magmas, and (2) aqueous transport and precipitation in thermal or fluid mixing gradients of isotopically heavy S, radiogenic Pb, and possibly other sedimentary pyrite and detrital mineral components, as sulfide minerals in intrusion-related metal deposits. A second mechanism invokes mixing and S isotope exchange in thermal aureoles of Pb and S exsolved from magma and derived from decomposition of sedimentary pyrite. A third mechanism entails melting of TDS strata or assimilation of TDS strata by crustal or mantle magmas. TDS-derived or assimilated magmas ascend, decompress, and exsolve a mixture of TDS volatiles, including isotopically heavy S and radiogenic Pb from sedimentary pyrite, and volatiles acquired from deeper crustal or mantle sources.In the central and eastern Great Basin, the wide distribution and high density of small to mid-sized vein, replacement, and skarn intrusion-related metal deposits in lower Paleozoic rocks that contain TDS sedimentary pyrite S and Pb reflect (1) prolific Jurassic, Cretaceous, and Tertiary magmatism, (2) a regional, substrate reservoir of S and Pb in permeable and homogeneous siliciclastic strata, and (3) relatively small scale concentration of substrate and magmatic components. Large intrusion-related metal deposits in the central and eastern Great Basin acquired S and most Pb from thicker lithospheric sections.

Growth of copper-benzene-1,3,5-tricarboxylate on boron nitride nanotubes and application of the composite in methane sensing

NASA Astrophysics Data System (ADS)

Xiang, Cuili; Chen, Ting; Zhang, Haitao; Zou, Yongjin; Chu, Hailiang; Zhang, Huanzhi; Xu, Fen; Sun, Lixian; Tang, Chengying

2017-12-01

A new composite material based on copper-benzene-1,3,5-tricarboxylate (Cu-BTC) deposited on boron nitride nanotubes (BNNTs) in a hydrothermal process were investigated for methane (CH4) sensing. The composite was characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The Cu-BTC deposited on the BNNTs had an average grain size of 80 nm. The sensing performance of the as-grown product was studied for different concentrations of CH4 (20-200 ppm) at 150 °C. The results revealed that the Cu-BTC/BNNT composite exhibited high sensitivity and selectivity toward CH4. The good sensing performance of the composite was attributed to the high surface area and high affinity of Cu-BTC for CH4, which would allow the composite to act like a preconcentrator for CH4 gas sensing.

Microcalorimetric and potentiometric titration studies on the adsorption of copper by P. putida and B. thuringiensis and their composites with minerals.

PubMed

Fang, Linchuan; Cai, Peng; Li, Pengxiang; Wu, Huayong; Liang, Wei; Rong, Xingmin; Chen, Wenli; Huang, Qiaoyun

2010-09-15

In order to have a better understanding of the interactions of heavy metals with bacteria and minerals in soil and associated environments, isothermal titration calorimetry (ITC), potentiometric titration and equilibrium sorption experiments were conducted to investigate the adsorption behavior of Cu(II) by Bacillus thuringiensis, Pseudomonas putida and their composites with minerals. The interaction of montmorillonite with bacteria increased the reactive sites and resulted in greater adsorption for Cu(II) on their composites, while decreased adsorption sites and capacities for Cu(II) were observed on goethite-bacteria composites. A gram-positive bacterium B. thuringiensis played a more important role than a gram-negative bacterium P. putida in determining the properties of the bacteria-minerals interfaces. The enthalpy changes (DeltaH(ads)) from endothermic (6.14 kJ mol(-1)) to slightly exothermic (-0.78 kJ mol(-1)) suggested that Cu(II) is complexed with the anionic oxygen ligands on the surface of bacteria-mineral composites. Large entropies (32.96-58.89 J mol(-1) K(-1)) of Cu(II) adsorption onto bacteria-mineral composites demonstrated the formation of inner-sphere complexes in the presence of bacteria. The thermodynamic data implied that Cu(II) mainly bound to the carboxyl and phosphoryl groups as inner-sphere complexes on bacteria and mineral-bacteria composites. Copyright 2010 Elsevier B.V. All rights reserved.

The post-Paleozoic chronology and mechanism of 13C depletion in primary marine organic matter

NASA Technical Reports Server (NTRS)

Popp, B. N.; Takigiku, R.; Hayes, J. M.; Louda, J. W.; Baker, E. W.

1989-01-01

Carbon-isotopic compositions of geoporphyrins have been measured from marine sediments of Mesozoic and Cenozoic age in order to elucidate the timing and extent of depletion of 13C in marine primary producers. These results indicate that the difference in isotopic composition of coeval marine carbonates and marine primary photosynthate was approximately 5 to 7 permil greater during the Mesozoic and early Cenozoic than at present. In contrast to the isotopic record of marine primary producers, isotopic compositions of terrestrial organic materials have remained approximately constant for this same interval of time. This difference in the isotopic records of marine and terrestrial organic matter is considered in terms of the mechanisms controlling the isotopic fractionation associated with photosynthetic fixation of carbon. We show that the decreased isotopic fractionation between marine carbonates and organic matter from the Early to mid-Cenozoic may record variations in the abundance of atmospheric CO2.

Zirconium isotope constraints on the composition of Theia and current Moon-forming theories

NASA Astrophysics Data System (ADS)

Akram, W.; Schönbächler, M.

2016-09-01

The giant impact theory is the most widely recognized formation scenario of the Earth's Moon. Giant impact models based on dynamical simulations predict that the Moon acquired a significant amount of impactor (Theia) material, which is challenging to reconcile with geochemical data for O, Si, Cr, Ti and W isotopes in the Earth and Moon. Three new giant impact scenarios have been proposed to account for this discrepancy - hit-and-run impact, impact with a fast-spinning protoEarth and massive impactors - each one reducing the proportion of the impactor in the Moon compared to the original canonical giant impact model. The validity of each theory and their different dynamical varieties are evaluated here using an integrated approach that considers new high-precision Zr isotope measurements of lunar rocks, and quantitative geochemical modelling of the isotopic composition of the impactor Theia. All analysed lunar samples (whole-rock, ilmenite and pyroxene separates) display identical Zr isotope compositions to that of the Earth within the uncertainty of 13 ppm for 96Zr/90Zr (2σ weighted average). This 13 ppm upper limit is used to infer the most extreme isotopic composition that Theia could have possessed, relative to the Earth, for each of the proposed giant impact theories. The calculated Theian composition is compared with the Zr isotope compositions of different solar system materials in order to constrain the source region of the impactor. As a first order approximation, we show that all considered models (including the canonical) are plausible, alleviating the initial requirement for the new giant impact models. Albeit, the canonical and hit-and-run models are the most restrictive, suggesting that the impactor originated from a region close to the Earth. The fast-spinning protoEarth and massive impactor models are more relaxed and increase the allowed impactor distance from the Earth. Similar calculations carried out for O, Cr, Ti and Si isotope data support these conclusions but exclude a CI- and enstatite chondrite-like composition for Theia. Thus, the impactor Theia most likely had a Zr isotope composition close to that of the Earth, and this suggests that a large part of the inner solar system (or accretion region of the Earth, Theia and enstatite chondrites) had a uniform Zr isotope composition.

Preparation and study of (1 - x)CuFe2O4-xBaTiO3 (x = 0, 0.1 and 1) composite multiferroics

NASA Astrophysics Data System (ADS)

Murtaza, Tahir; Ali, Javid; Khan, M. S.

2018-07-01

The parent and mixed spinel-perovskite composite of (1 - x)CuFe2O4-xBaTiO3 (x = 0, 0.1 and 1) has been prepared by solid-state reaction method and studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), Mössbauer spectroscopy, magnetometry and P-E lope tracer. The XRD results showed the formation of single phase tetragonal spinel CuFe2O4 and tetragonal perovskite BaTiO3 at room temperature, further XRD of composite 0.1CuFe2O4-0.9BaTiO3 reflects the two crystallographic phases with 1:9 ratio. The SEM micrographs show the homogeneous and uniform formation of the samples. Through EDAX analysis, the chemical composition of the sample is found to be same as the nominal composition. The high field Mossbauer data of CuFe2O4 sample shows the ferrimagnetic ordering in the sample. The observed M-H and P-E loops of the composite 0.1CuFe2O4-0.9BaTiO3 sample show the presence of spontaneous magnetization and spontaneous electric polarization indicating the multiferroic nature of the sample.

Isotopic compositions of cometary matter returned by Stardust.

PubMed

McKeegan, Kevin D; Aléon, Jerome; Bradley, John; Brownlee, Donald; Busemann, Henner; Butterworth, Anna; Chaussidon, Marc; Fallon, Stewart; Floss, Christine; Gilmour, Jamie; Gounelle, Matthieu; Graham, Giles; Guan, Yunbin; Heck, Philipp R; Hoppe, Peter; Hutcheon, Ian D; Huth, Joachim; Ishii, Hope; Ito, Motoo; Jacobsen, Stein B; Kearsley, Anton; Leshin, Laurie A; Liu, Ming-Chang; Lyon, Ian; Marhas, Kuljeet; Marty, Bernard; Matrajt, Graciela; Meibom, Anders; Messenger, Scott; Mostefaoui, Smail; Mukhopadhyay, Sujoy; Nakamura-Messenger, Keiko; Nittler, Larry; Palma, Russ; Pepin, Robert O; Papanastassiou, Dimitri A; Robert, François; Schlutter, Dennis; Snead, Christopher J; Stadermann, Frank J; Stroud, Rhonda; Tsou, Peter; Westphal, Andrew; Young, Edward D; Ziegler, Karen; Zimmermann, Laurent; Zinner, Ernst

2006-12-15

Hydrogen, carbon, nitrogen, and oxygen isotopic compositions are heterogeneous among comet 81P/Wild 2 particle fragments; however, extreme isotopic anomalies are rare, indicating that the comet is not a pristine aggregate of presolar materials. Nonterrestrial nitrogen and neon isotope ratios suggest that indigenous organic matter and highly volatile materials were successfully collected. Except for a single (17)O-enriched circumstellar stardust grain, silicate and oxide minerals have oxygen isotopic compositions consistent with solar system origin. One refractory grain is (16)O-enriched, like refractory inclusions in meteorites, suggesting that Wild 2 contains material formed at high temperature in the inner solar system and transported to the Kuiper belt before comet accretion.

Isotopic Analysis and Evolved Gases

NASA Technical Reports Server (NTRS)

Swindle, Timothy D.; Boynton, William V.; Chutjian, Ara; Hoffman, John H.; Jordan, Jim L.; Kargel, Jeffrey S.; McEntire, Richard W.; Nyquist, Larry

1996-01-01

Precise measurements of the chemical, elemental, and isotopic composition of planetary surface material and gases, and observed variations in these compositions, can contribute significantly to our knowledge of the source(s), ages, and evolution of solar system materials. The analyses discussed in this paper are mostly made by mass spectrometers or some other type of mass analyzer, and address three broad areas of interest: (1) atmospheric composition - isotopic, elemental, and molecular, (2) gases evolved from solids, and (3) solids. Current isotopic data on nine elements, mostly from in situ analysis, but also from meteorites and telescopic observations are summarized. Potential instruments for isotopic analysis of lunar, Martian, Venusian, Mercury, and Pluto surfaces, along with asteroid, cometary and icy satellites, surfaces are discussed.

Approaches to Plant Hydrogen and Oxygen Isoscapes Generation

DOE Office of Scientific and Technical Information (OSTI.GOV)

West, Jason B.; Kreuzer-Martin, Helen W.; Ehleringer, James

2009-12-01

Plant hydrogen and oxygen isoscapes have been utilized to address important and somewhat disparate research goals. The isotopic composition of leaf water affects the isotopic composition of atmospheric CO2 and O2 and is a logical starting point for understanding the isotopic composition of plant organic compounds since photosynthesis occurs in the leaf water environment. Leaf water isoscapes have been produced largely as part of efforts to understand atmospheric gas isotopic composition. The isotopic composition of plant organic matter has also been targeted for its potential to serve as a proxy for past environmental conditions. Spatially distributed sampling and modeling ofmore » modern plant H & O isoscapes can improve our understanding of the controls of the isotope ratios of compounds such as cellulose or n-alkanes from plants and therefore their utility for paleoreconstructions. Spatially varying plant hydrogen and oxygen isotopes have promise for yielding geographic origin information for a variety of plant products, including objects of criminal forensic interest or food products. The future has rich opportunities for the continued development of mechanistic models, methodologies for the generation of hydrogen and oxygen isoscapes, and cross-disciplinary interactions as these tools for understanding are developed, shared, and utilized to answer large-scale questions.« less

A IAB-Complex Iron Meteorite Containing Low-Ca Clinopyroxene: Northwest Africa 468 and its Relationship to Iodranites and Formation by Impact Melting

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Kallemeyn, Gregory W.; Wasson, John T.

2002-01-01

Northwest Africa 468 (NWA 468) is a new ungrouped, silicate-rich member of the IAB complex of nonmagmatic iron meteorites. The silicates contain relatively coarse (approximately 300 micron-size) grains of low-Ca clinopyroxene with polysynthetic twinning and inclined extinction. Low-Ca clinopyroxene is indicative of quenching from high temperatures (either from protoenstatite in a few seconds or high-temperature clinoenstatite in a few hours). It seems likely that NWA 468 formed by impact melting followed by rapid cooling to less than or equal to 660 C. After the loss of a metal-sulfide melt from the silicates, sulfide was reintroduced, either from impact-mobilized FeS or as an S2 vapor that combined with metallic Fe to produce FeS. The O-isotopic composition (delta O-17 = -1.39 %) indicates that the precursor material of NWA 468 was a metal-rich (e.g., CR) carbonaceous chondrite. Lodranites are similar in bulk chemical and O-isotopic composition to the silicates in NWA 468; the MAC 88177 lodranite (which also contains low-Ca clinopyroxene) is close in bulk chemical composition. Both NWA 468 and MAC 88177 have relatively low abundances of REE (rare earth elements) and plagiophile elements. Siderophiles in the metal-rich areas of NWA 468 are similar to those in the MAC 88177 whole rock; both samples contain low Ir and relatively high Fe, Cu and Se. Most unweathered lodranites contain approximately 20 - 38 wt. % metallic Fe-Ni. These rocks may have formed in an analogous manner to NWA 468 (i.e., by impact melting of metal-rich carbonaceous-chondrite precursors) but with less separation of metal-rich melts from silicates.

Multielement statistical evidence for uraniferous hydrothermal activity in sandstones overlying the Phoenix uranium deposit, Athabasca Basin, Canada

NASA Astrophysics Data System (ADS)

Chen, Shishi; Hattori, Keiko; Grunsky, Eric C.

2018-04-01

The Phoenix U deposit, with indicated resources of 70.2 M lb U3O8, occurs along the unconformity between the Proterozoic Athabasca Group sandstones and the crystalline basement rocks. Principal component analysis (PCA) is applied to the compositions of sandstones overlying the deposit. Among PCs, PC1 accounts for the largest variability of U and shows a positive association of U with rare earth elements (REEs) + Y + Cu + B + Na + Mg + Ni + Be. The evidence suggests that U was dispersed into sandstones together with these elements during the uraniferous hydrothermal activity. Uranium shows an inverse association with Zr, Hf, Th, Fe, and Ti. Since they are common in detrital heavy minerals, such heavy minerals are not the major host of U. The elements positively associated with U are high in concentrations above the deposit, forming a "chimney-like" or "hump-like" distribution in a vertical section. Their enrichment patterns are explained by the ascent of basement fluids through faults to sandstones and the circulation of basinal fluids around the deposit. The Pb isotope compositions of whole rocks are similar to expected values calculated from the concentrations of U, Th, and Pb except for sandstones close to the deposit. The data suggest that in situ decay of U and Th is responsible for the Pb isotope compositions of most sandstones and that highly radiogenic Pb dispersed from the deposit to the proximal sandstones long after the mineralization. This secondary dispersion is captured in PC8, which has low eigenvalue. The data suggests that the secondary dispersion has minor effect on the overall lithogeochemistry of sandstones.

Synthesis and radiolabeling of a somatostatin analog for multimodal imaging

NASA Astrophysics Data System (ADS)

Edwards, W. Barry; Liang, Kexian; Xu, Baogang; Anderson, Carolyn J.; Achilefu, Samuel

2006-02-01

A new multimodal imaging agent for imaging the somatostatin receptor has been synthesized and evaluated in vitro and in vivo. A somatostatin analog, conjugated to both 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraaceticacid (DOTA) and cypate (BS-296), was synthesized entirely on the solid phase (Fmoc) and purified by RP-HPLC. DOTA was added as a ligand for radiometals such as 64Cu or 177Lu for either radio-imaging or radiotherapy respectively. Cytate, a cypatesomatostatin analog conjugate, has previously demonstrated the ability to visualize somatostatin receptor rich tumor xenografts and natural organs by optical imaging techniques. BS-296 exhibited low nanomolar inhibitory capacity toward the binding of radiolabeled somatostatin analogs in cell membranes enriched in the somatostatin receptor, demonstrating the high affinity of this multimodal imaging peptide and indicating its potential as a molecular imaging agent. 64Cu, an isotope for diagnostic imaging and radiotherapy, was selected as the isotope for radiolabeling BS-296. BS-296 was radiolabeled with 64Cu in high specific activity (200 μCi/μg) in 90% radiochemical yield. Addition of 2,5-dihydroxybenzoic acid (gentisic acid) prevented radiolysis of the sample, allowing for study of the 64Cu -BS-296 the day following radiolabeling. Furthermore, inclusion of DMSO at a level of 20% was found not to interfere with radiolabeling yields and prevented the adherence of 64Cu -BS-296 to the walls of the reaction vessel.

The evolution of 13C and 18O isotope composition of DIC in a calcite depositing film of water with isotope exchange between the DIC and a CO2 containing atmosphere, and simultaneous evaporation of the water. Implication to climate proxies from stalagmites: A theoretical model

NASA Astrophysics Data System (ADS)

Dreybrodt, Wolfgang; Romanov, Douchko

2016-12-01

The most widely applied climate proxies in speleothems are the isotope compositions of carbon and oxygen expressed by δ13C and δ18O values. However, mechanisms, which are not related to climate changes, overlay the climate signal. One is the temporal increase of both, δ13C and δ18O values by kinetic processes during precipitation of calcite. Isotope exchange between DIC in the water and the CO2 in the surrounding cave atmosphere can also change isotope composition. Here we present a theoretical model of the temporal isotope evolution of DIC in a thin water layer during precipitation of calcite and simultaneous isotope exchange with the cave atmosphere, and simultaneous evaporation of water. The exchange of oxygen isotopes in the DIC with those in the water is also considered.

Contrasting fluids and reservoirs in the contiguous Marcona and Mina Justa iron oxide-Cu (-Ag-Au) deposits, south-central Perú

NASA Astrophysics Data System (ADS)

Chen, Huayong; Kyser, T. Kurtis; Clark, Alan H.

2011-10-01

The Marcona-Mina Justa deposit cluster, hosted by Lower Paleozoic metaclastic rocks and Middle Jurassic shallow marine andesites, incorporates the most important known magnetite mineralization in the Andes at Marcona (1.9 Gt at 55.4% Fe and 0.12% Cu) and one of the few major iron oxide-copper-gold (IOCG) deposits with economic Cu grades (346.6 Mt at 0.71% Cu, 3.8 g/t Ag and 0.03 g/t Au) at Mina Justa. The Middle Jurassic Marcona deposit is centred in Ica Department, Perú, and the Lower Cretaceous Mina Justa Cu (Ag, Au) prospect is located 3-4 km to the northeast. New fluid inclusion studies, including laser ablation time-of-flight inductively coupled plasma mass spectrometry (LA-TOF-ICPMS) analysis, integrated with sulphur, oxygen, hydrogen and carbon isotope analyses of minerals with well-defined paragenetic relationships, clarify the nature and origin of the hydrothermal fluid responsible for these contiguous but genetically contrasted deposits. At Marcona, early, sulphide-free stage M-III magnetite-biotite-calcic amphibole assemblages are inferred to have crystallized from a 700-800°C Fe oxide melt with a δ18O value from +5.2‰ to +7.7‰. Stage M-IV magnetite-phlogopite-calcic amphibole-sulphide assemblages were subsequently precipitated from 430-600°C aqueous fluids with dominantly magmatic isotopic compositions (δ34S = +0.8‰ to +5.9‰; δ18O = +9.6‰ to +12.2‰; δD = -73‰ to -43‰; and δ13C = -3.3‰). Stages M-III and M-IV account for over 95% of the magnetite mineralization at Marcona. Subsequent non-economic, lower temperature sulphide-calcite-amphibole assemblages (stage M-V) were deposited from fluids with similar δ34S (+1.8‰ to +5.0‰), δ18O (+10.1‰ to +12.5‰) and δ13C (-3.4‰), but higher δD values (average -8‰). Several groups of lower (<200°C, with a mode at 120°C) and higher temperature (>200°C) fluids can be recognized in the main polymetallic (Cu, Zn, Pb) sulphide stage M-V and may record the involvement of modified seawater. At Mina Justa, early magnetite-pyrite assemblages precipitated from a magmatic fluid (δ34S = +0.8‰ to +3.9‰; δ18O = +9.5‰ to +11.5‰) at 540-600°C, whereas ensuing chalcopyrite-bornite-digenite-chalcocite-hematite-calcite mineralization was the product of non-magmatic, probably evaporite-sourced, brines with δ34S ≥ +29‰, δ18O = 0.1‰ and δ13C = -8.3‰. Two groups of fluids were involved in the Cu mineralization stage: (1) Ca-rich, low-temperature (approx. 140°C) and high-salinity, plausibly a basinal brine and (2) Na (-K)-dominant with a low-temperature (approx. 140°C) and low-salinity probably meteoric water. LA-TOF-ICPMS analyses show that fluids at the magnetite-pyrite stage were Cu-barren, but that those associated with external fluids in later stages were enriched in Cu and Zn, suggesting such fluids could have been critical for the economic Cu mineralization in Andean IOCG deposits.

Cu(II) removal by Anoxybacillus flavithermus-iron oxide composites during the addition of Fe(II)aq

NASA Astrophysics Data System (ADS)

Franzblau, Rachel E.; Daughney, Christopher J.; Swedlund, Peter J.; Weisener, Christopher G.; Moreau, Magali; Johannessen, Bernt; Harmer, Sarah L.

2016-01-01

There is currently poor understanding of metal removal by composites of bacteria and iron oxide minerals, even though they commonly co-occur and are among the most important sorbents in near-surface fluid-rock environments. This study evaluated Cu removal by composites of Anoxybacillus flavithermus and iron oxide over time during the addition, oxidation, and hydrolysis of Fe(II)aq and precipitation of the mineral, in comparison to Cu removal in the two single-sorbent end-member systems. In the absence of iron oxide, Cu removal by A. flavithermus was well described by a previously published surface complexation model, after inclusion of additional reactions describing aqueous complexation by exudate ligands released by the bacteria. In the absence of bacterial cells, Cu removal by iron oxide synthesized in the presence of the bacterial exudate ligands demonstrated the formation of ternary surface complexes. Removal of Cu by the A. flavithermus-iron oxide composites was ca. 20% greater than the prediction based on assumption of additivity in the two end-member systems. This non-additive behavior was attributed to (1) progressive physical blockage of bacterial surface sites by the iron oxide particles, (2) physical blockage of adsorption sites as a result of self-aggregation of the iron oxide particles, and (3) the reduction of Cu(II) to Cu(I) at the bacterial cell surface, as demonstrated by X-ray absorption spectroscopy. The extent of reduction of Cu(II) to Cu(I) was proportional to the concentration of solid phase Fe(II), suggesting that iron oxidation and copper reduction are linked. This study has shown that Cu removal by bacteria-iron oxide composites is greatly affected by redox processes such as Cu(II) reduction on the cell surface both by other bacterial surface ligands and the oxidation of sorbed Fe(II), as well as Fe(II) redox interactions, and aging effects of the mineral (i.e. surface site masking).

Heterogeneity of the Caribbean plateau mantle source: Sr, O and He isotopic compositions of olivine and clinopyroxene from Gorgona Island

NASA Astrophysics Data System (ADS)

Révillon, S.; Chauvel, C.; Arndt, N. T.; Pik, R.; Martineau, F.; Fourcade, S.; Marty, B.

2002-12-01

The composition of the mantle plumes that created large oceanic plateaus such as Ontong Java or the Caribbean is still poorly known. Geochemical and isotopic studies on accreted portions of the Caribbean plateau have shown that the plume source was heterogeneous and contained isotopically depleted and relatively enriched portions. A distinctive feature of samples from the Caribbean plateau is their unusual Sr isotopic compositions, which, at a given Nd isotopic ratio, are far higher than in samples from other oceanic plateaus. Sr, O and He isotopic compositions of whole rocks and magmatic minerals (clinopyroxene or olivine) separated from komatiites, gabbros and peridotites from Gorgona Island in Colombia were determined to investigate the origin of these anomalously radiogenic compositions. Sequentially leached clinopyroxenes have Sr isotopic compositions in the range 87Sr/ 86Sr=0.70271-0.70352, systematically lower than those of leached and unleached whole rocks. Oxygen isotopic ratios of clinopyroxene vary within the range δ 18O=5.18-5.35‰, similar to that recorded in oceanic island basalts. He isotopic ratios are high ( R/ Ra=8-19). The lower 87Sr/ 86Sr ratios of most of the clinopyroxenes shift the field of the Caribbean plateau in Nd-Sr isotope diagrams toward more 'normal' values, i.e. a position closer to the field defined by mid-ocean ridge basalts and oceanic-island basalts. Three clinopyroxenes have slightly higher 87Sr/ 86Sr ratios that cannot be explained by an assimilation model. The high 87Sr/ 86Sr and variations of 143Nd/ 144Nd are interpreted as a source characteristic. Trace-element ratios, however, are controlled mainly by fractionation during partial melting. We combine these isotopic data in a heterogeneous plume source model that accounts for the diversity of isotopic signatures recorded on Gorgona Island and throughout the Caribbean plateau. The heterogeneities are related to old recycled oceanic lithosphere in the plume source; the high 3He/ 4He ratios may indicate that the source material once resided in the lower mantle.

Nd Isotope and U-Th-Pb Age Mapping of Single Monazite Grains by Laser Ablation Split Stream Analysis

NASA Astrophysics Data System (ADS)

Fisher, C. M.; Hanchar, J. M.; Miller, C. F.; Phillips, S.; Vervoort, J. D.; Martin, W.

2015-12-01

Monazite is a common accessory mineral that occurs in medium to high grade metamorphic and Ca-poor felsic igneous rocks, and often controls the LREE budget (including Sm and Nd) of the host rock in which it crystallizes. Moreover, it contains appreciable U and Th, making it an ideal mineral for determining U-Th-Pb ages and Sm-Nd isotopic compositions, both of which are readily determined using in situ techniques with very high spatial resolution like LA-MC-ICPMS. Here, we present the results of laser ablation split stream analyses (LASS), which allows for simultaneous determination of the age and initial Nd isotopic composition in a single analysis. Analyses were done using a 20mm laser spot that allowed for detailed Nd isotope mapping of monazite grains (~30 analyses per ~250mm sized grain). Combined with LREE ratios (e.g., Sm/Nd, Ce/Gd, and Eu anomalies) these results yield important petrogenetic constraints on the evolution of peraluminous granites from the Old Woman-Piute batholith in southeastern California. Our findings also allow an improved understanding of the causes of isotope heterogeneity in granitic rocks. U-Th-Pb age mapping across the crystals reveals a single Cretaceous age for all grains with precision and accuracy typical of laser ablation analyses (~2%). In contrast, the concurrent Nd isotope mapping yields homogeneous initial Nd isotope compositions for some grains and large initial intra-grain variations of up to 8 epsilon units in others. The grains that yield homogeneous Nd isotope compositions have REE ratios suggesting that they crystallized in a fractionally crystallizing magma. Conversely, other grains, which also record fractional crystallization of both feldspar and LREE rich minerals, demonstrate a change in the Nd isotope composition of the magma during crystallization of monazite. Comparison of inter- and intra-grain Nd isotope compositions reveals further details on the potential mechanisms responsible for isotope heterogeneity present in single rock samples. This method highlights the potential of single grain isotope mapping of LREE phases such as monazite, allanite, and titanite for understanding both igneous and metamorphic petrogenesis.

Isotopic inferences of ancient biochemistries - Carbon, sulfur, hydrogen, and nitrogen

NASA Technical Reports Server (NTRS)

Schidlowski, M.; Hayes, J. M.; Kaplan, I. R.

1983-01-01

In processes of biological incorporation and subsequent biochemical processing sizable isotope effects occur as a result of both thermodynamic and kinetic fractionations which take place during metabolic and biosynthetic reactions. In this chapter a review is provided of earlier work and recent studies on isotope fractionations in the biogeochemical cycles of carbon, sulfur, hydrogen, and nitrogen. Attention is given to the biochemistry of carbon isotope fractionation, carbon isotope fractionation in extant plants and microorganisms, isotope fractionation in the terrestrial carbon cycle, the effects of diagenesis and metamorphism on the isotopic composition of sedimentary carbon, the isotopic composition of sedimentary carbon through time, implications of the sedimentary carbon isotope record, the biochemistry of sulfur isotope fractionation, pathways of the biogeochemical cycle of nitrogen, and the D/H ratio in naturally occurring materials.

Light triggered interfacial damage self-healing of poly(p-phenylene benzobisoxazole) fiber composites.

PubMed

Hu, Zhen; Shao, Qing; Huang, Yudong; Yu, Long; Zhang, Dayu; Xu, Xirong; Lin, Jing; Liu, Hu; Guo, Zhanhu

2018-05-04

The interfacial microcracks in the resin matrix composites are difficult to be detected and repaired. However, the self-healing concept provides opportunities to fabricate composites with unusual properties. In the present study, photothermal conversion Ag-Cu 2 S nanoparticles were immobilized onto poly(p-phenylene benzobisoxazole) (PBO) fibers via a polydopamine chemistry. Benefitting from the photothermal effects of Ag-Cu 2 S, the obtained PBO fibers (Ag-Cu 2 S-PBO) efficiently converted the light energy into heat under Xenon lamp irradiation. Then, single PBO fiber composites were prepared using thermoplastic polyurethane as the matrix. It was found that the interfacial damage caused by single fiber pull-out was simply self-healed by Xe light irradiation. This wonderful interfacial damage self-healing property was mainly attributed to the in situ heating generation via photothermal effects of Ag-Cu 2 S in the composite interface. This paper reports a novel strategy to construct advanced composites with light-triggered self-healing properties, which will provide inspiration for preparing high performance composite materials.

Light triggered interfacial damage self-healing of poly(p-phenylene benzobisoxazole) fiber composites

NASA Astrophysics Data System (ADS)

Hu, Zhen; Shao, Qing; Huang, Yudong; Yu, Long; Zhang, Dayu; Xu, Xirong; Lin, Jing; Liu, Hu; Guo, Zhanhu

2018-05-01

The interfacial microcracks in the resin matrix composites are difficult to be detected and repaired. However, the self-healing concept provides opportunities to fabricate composites with unusual properties. In the present study, photothermal conversion Ag-Cu2S nanoparticles were immobilized onto poly(p-phenylene benzobisoxazole) (PBO) fibers via a polydopamine chemistry. Benefitting from the photothermal effects of Ag-Cu2S, the obtained PBO fibers (Ag-Cu2S-PBO) efficiently converted the light energy into heat under Xenon lamp irradiation. Then, single PBO fiber composites were prepared using thermoplastic polyurethane as the matrix. It was found that the interfacial damage caused by single fiber pull-out was simply self-healed by Xe light irradiation. This wonderful interfacial damage self-healing property was mainly attributed to the in situ heating generation via photothermal effects of Ag-Cu2S in the composite interface. This paper reports a novel strategy to construct advanced composites with light-triggered self-healing properties, which will provide inspiration for preparing high performance composite materials.

Fabrication of nanocrystalline surface composite layer on Cu plate under ball collisions.

PubMed

Romankov, S; Park, Y C; Yoon, J M

2014-10-01

It was demonstrated that the severe plastic deformation of a surface induced by repeated ball collisions can be effectively used for fabrication of the nanocrystalline surface composite layers. The Cu disk was fixed at the top of a vibration chamber and ball treated. Al, Zr, Ni, Co and Fe were introduced into a Cu plate as contaminants from the grinding media one after the other by 15-min ball treatment. The composite structure was formed as a result of mechanical intermixing of the components. The particle size in as-fabricated layer ranged from 2 nm to 20 nm, with average values of about 7 nm. As-fabricated layer contained non-equilibrium multicomponent solid solution based on FCC Cu crystal structure, Zr-based phase, nanosized steel debris and amorphous phase. The hardness of the as-fabricated composite was almost ten times that of the initial Cu plate.

Investigation of Pd-Modified Ag-CuO Air Braze Filler Metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Darsell, Jens T.; Hardy, John S.; Kim, Jin Yong

2006-01-10

Palladium was added as a ternary component to a series of silver - copper oxide alloys in an effort to increase the use temperature of these materials for potential ceramic air brazing applications. Large portions of the silver component of the Ag-CuO system were substituted by palladium forming the following alloys: (100-y)[(100-z)Pd - (z)Ag] - (y)CuOx where y = 0 - 34 mol% CuOx, z = 50 - 100 mol% silver, and x = 0, 0.5, and 1, denoting copper metal, Cu2O, or CuO. From differential scanning calorimetry, it was determined that the addition of palladium causes an increase inmore » the solidus and liquidus temperatures of the resulting Pd-Ag-CuO brazes. In general, the liquidus was found to increase by approximately 220°C for the (100-y)(25Pd - 75Ag) - (z)CuOx filler metal compositions relative to comparable Ag-CuOx alloys. Likewise, the solidus was found to increase for these alloys, respectively by 185°C and 60°C, respectively for CuOx contents of y = 0 - 1mol% and 4 - 10 mol%. For the (100-y)(50Pd - 50Ag) - (y)CuOx alloys, the solidus increased between 280 - 390°C over a copper oxide compositional range of x = 0 to 8 mol%. It was determined from sessile drop experiments that palladium causes an increase in the wetting angle for all of the samples tested. Alloy compositions of (100-y)(25Pd - 75Ag) - (y)CuOx displayed increased wetting angles of 5-20° relative to comparable binary compositions. (100-y)(50Pd - 50Ag) - (y)CuOx alloys exhibited an increase in contact angle of 10-60° and compositions containing less than 10 mol% CuOx were not able to wet the substrate. Scanning electron microscopy indicates that the microstructure of the braze consists of Ag-Pd solid solution with CuOx precipitates. In general, a reaction layer consisting of CuAlO2 forms adjacent to the alumina substrate. However, the formation of this layer is apparently hindered by the addition of large amounts of palladium, causing poor wetting behavior, as denoted by substantial porosity found along the braze/substrate interface. The reduction in wettability can be compensated by increasing the CuO content slightly.« less

Design of flexible PANI-coated CuO-TiO2-SiO2 heterostructure nanofibers with high ammonia sensing response values

NASA Astrophysics Data System (ADS)

Pang, Zengyuan; Nie, Qingxin; Lv, Pengfei; Yu, Jian; Huang, Fenglin; Wei, Qufu

2017-06-01

We report a room-temperature ammonia sensor with extra high response values and ideal flexibility, including polyaniline (PANI)-coated titanium dioxide-silicon dioxide (TiO2-SiO2) or copper oxide-titanium dioxide-silicon dioxide (CuO-TiO2-SiO2) composite nanofibers. Such flexible inorganic TiO2-SiO2 and CuO-TiO2-SiO2 composite nanofibers were prepared by electrospinning, followed by calcination. Then, in situ polymerization of aniline monomers was carried out with inorganic TiO2-SiO2 and CuO-TiO2-SiO2 composite nanofibers as templates. Gas sensing tests at room temperature indicated that the obtained CuO-TiO2-SiO2/PANI composite nanofibers had much higher response values to ammonia gas (ca. 45.67-100 ppm) than most of those reported before as well as the prepared TiO2-SiO2/PANI composite nanofibers here. These excellent sensing properties may be due to the P-N, P-P heterojunctions and a structure similar to field-effect transistors formed on the interfaces between PANI, TiO2, and CuO, which is p-type, n-type, and p-type semiconductor, respectively. In addition, the prepared free-standing CuO-TiO2-SiO2/PANI composite nanofiber membrane was easy to handle and possessed ideal flexibility, which is promising for potential applications in wearable sensors in the future.

Design of flexible PANI-coated CuO-TiO2-SiO2 heterostructure nanofibers with high ammonia sensing response values.

PubMed

Pang, Zengyuan; Nie, Qingxin; Lv, Pengfei; Yu, Jian; Huang, Fenglin; Wei, Qufu

2017-06-02

We report a room-temperature ammonia sensor with extra high response values and ideal flexibility, including polyaniline (PANI)-coated titanium dioxide-silicon dioxide (TiO 2 -SiO 2 ) or copper oxide-titanium dioxide-silicon dioxide (CuO-TiO 2 -SiO 2 ) composite nanofibers. Such flexible inorganic TiO 2 -SiO 2 and CuO-TiO 2 -SiO 2 composite nanofibers were prepared by electrospinning, followed by calcination. Then, in situ polymerization of aniline monomers was carried out with inorganic TiO 2 -SiO 2 and CuO-TiO 2 -SiO 2 composite nanofibers as templates. Gas sensing tests at room temperature indicated that the obtained CuO-TiO 2 -SiO 2 /PANI composite nanofibers had much higher response values to ammonia gas (ca. 45.67-100 ppm) than most of those reported before as well as the prepared TiO 2 -SiO 2 /PANI composite nanofibers here. These excellent sensing properties may be due to the P-N, P-P heterojunctions and a structure similar to field-effect transistors formed on the interfaces between PANI, TiO 2 , and CuO, which is p-type, n-type, and p-type semiconductor, respectively. In addition, the prepared free-standing CuO-TiO 2 -SiO 2 /PANI composite nanofiber membrane was easy to handle and possessed ideal flexibility, which is promising for potential applications in wearable sensors in the future.

Mechanical Characterization and Micromechanical Modeling of Woven Carbon/Copper Composites

NASA Technical Reports Server (NTRS)

Bednarcyk, Brett A.; Pindera, Marek-Jerzy; Ellis, David L.; Miner, Robert V.

1997-01-01

The present investigation examines the in-plane mechanical behavior of a particular woven metal matrix composite (MMC); 8-harness (8H) satin carbon/copper (C/Cu). This is accomplished via mechanical testing as well as micromechanical modeling. While the literature is replete with experimental and modeling efforts for woven and braided polymer matrix composites, little work has been done on woven and braided MMC's. Thus, the development and understanding of woven MMC's is at an early stage. 8H satin C/Cu owes its existence to the high thermal conductivity of copper and low density and thermal expansion of carbon fibers. It is a candidate material for high heat flux applications, such as space power radiator panels. The experimental portion of this investigation consists of monotonic and cyclic tension, compression, and Iosipescu shear tests, as well as combined tension-compression tests. Tests were performed on composite specimens with three copper matrix alloy types: pure Cu, Cu-0.5 weight percent Ti (Cu-Ti), and Cu-0.7 weight percent Cr (Cu-Cr). The small alloying additions are present to promote fiber/matrix interfacial bonding. The analytical modeling effort utilizes an approach in which a local micromechanical model is embedded in a global micromechanical model. This approach differs from previously developed analytical models for woven composites in that a true repeating unit cell is analyzed. However, unlike finite element modeling of woven composites, the geometry is sufficiently idealized to allow efficient geometric discretization and efficient execution.

Isotopic compositions of the elements 2013 (IUPAC Technical Report)

USGS Publications Warehouse

Meija, Juris; Coplen, Tyler B.; Berglund, Michael; Brand, Willi A.; De Bièvre, Paul; Gröning, Manfred; Holden, Norman E.; Irrgeher, Johanna; Loss, Robert D.; Walczyk, Thomas; Prohaska, Thomas

2016-01-01

The Commission on Isotopic Abundances and Atomic Weights (ciaaw.org) of the International Union of Pure and Applied Chemistry (iupac.org) has revised the Table of Isotopic Compositions of the Elements (TICE). The update involved a critical evaluation of the recent published literature. The new TICE 2013 includes evaluated data from the “best measurement” of the isotopic abundances in a single sample, along with a set of representative isotopic abundances and uncertainties that accommodate known variations in normal terrestrial materials.

Relationship between the trajectory of mid-latitude cyclones in the eastern Pacific Ocean and the isotopic composition of snowfall in the Sierra Nevada, California

NASA Astrophysics Data System (ADS)

Vasquez, K. T.; Sickman, J. O.; Heard, A.; Lucero, D.

2013-12-01

Diatoms, preserved in lake sediments, provide a potential archive of snowfall variability in the Sierra Nevada through their sensitivity to changes in water chemistry (a proxy for runoff volume) and by recording the isotopic composition of snow-melt (potentially a proxy for sources of atmospheric moisture). In the Sierra Nevada, we hypothesize that the oxygen isotopic composition of diatom silica is principally controlled by snow and that the isotopic composition of snow varies as a function of the tracks of mid-latitude cyclonic storms in the eastern Pacific Ocean. Snow samples from discrete storms were collected from December 2012 to March 2013 at 2042 meters a.s.l. in Sequoia National Park. The δ18O and δ2H values of the snow samples were measured using a temperature-conversion elemental analyzer coupled to a Delta V isotope ratio mass spectrometer. The isotopic measurements were then coupled to 3, 5 and 7-day air mass back trajectories using the NOAA HYSPLIT model. The measured δ18O values ranged from -17.6 to -7.8 per mil and the δ2H ranged from -119.8 to -73.3 per mil. Both δ18O and δ2H were inversely related to the latitude of the storm origin (R^2 values of 0.67 and 0.57, respectively). Winter storms from the Gulf of Alaska were the most isotopically depleted while storms originating in the subtropical/tropical Pacific were the most isotopically enriched, reflecting the overall latitudinal pattern of ocean-water isotope composition in the Pacific Ocean. Our results suggest that the isotopic composition of Sierra Nevada snowfall is influenced by storm track trajectory and this relationship could be useful in interpreting the climatic significance of δ18O of diatom silica preserved in lake cores.

Overview and Brief History of the Boron Isotope Proxy for Past Seawater pH

NASA Astrophysics Data System (ADS)

Hoenisch, B.; Hemming, G.

2007-05-01

In 1992 Hemming and Hanson (GCA, vol. 56, p. 537-543) showed that a variety of modern marine carbonates revealed a boron isotopic composition close to the isotopic composition of dissolved borate at modern seawater pH, suggesting this was the boron species preferentially adsorbed and incorporated into marine carbonates. With a constant offset between the trigonal and tetrahedrally coordinated boron species and a pH-dependent variation in their fractions, it appeared that this system would be sensitive to pH changes in the natural range of seawater. Accordingly, it was suggested that the boron isotope composition of marine carbonates is a proxy for past seawater pH. Subsequent culture studies with living planktic foraminifers and corals, as well as synthetic precipitation experiments confirmed that the boron isotopic composition follows the isotopic composition of borate across a wide range of seawater pH. In order to use the proxy with confidence, however, all other controls apart from pH need to be thoroughly understood. Recent laboratory and sediment experiments have demonstrated that vital effects and partial shell dissolution have the potential to modify the primary seawater pH signal recorded in the boron isotopic composition of planktic foraminifers. However it has also been shown that careful sample selection allows for avoiding these potential complications. A record of reconstructed surface seawater pH and estimated aqueous PCO2 shows a remarkable match between boron isotope based atmospheric pCO2 estimates and the Vostok ice core CO2 record. This convincingly demonstrates that boron isotopes in planktic foraminifers allow quantitative estimates of atmospheric pCO2 in the past, and confirms that glacial surface ocean pH was ~0.2 units higher compared to interglacial periods. We are going to review and discuss the achievements generated in Gil Hanson's lab over the past 15 years in the light of recent empirical measurements of the boron isotope fractionation between boric acid and borate in seawater.

Calibrating NIST SRM 683 as A New International Reference Standard for Zn Isotopes

NASA Astrophysics Data System (ADS)

Yang, Y.; Zhang, X.; Yu, H.; Huang, F.

2017-12-01

Zinc isotopes have been widely applied in the cosmochemical, geochemical, and environmental studies (Moynier et al. 2017). Obtaining precise Zn isotopic data for inter-laboratory comparison is a prerequisite to these applications. Currently, the JMC3-0749L is the primary reference standard for Zn isotopes (Albarède 2004), but it is not commercially available now. Thus, it is necessary to calibrate a new international primary reference standard for Zn isotopic analysis. Chen et al. (2016) showed that NIST SRM 683 (a pure Zn metal nugget of 140 grams) has a δ66ZnJMC of 0.12‰, which is falling within the range of natural Zn isotopic compositions, and it may a good candidate for the next generation of international reference standard (Chen et al. 2016). In order to further examine whether NIST SRM 683 has a homogeneous Zn isotopic composition, we measured more NIST SRM 683 by double-spike methods using MC-ICPMS (Conway et al. 2013). The metal nuggets of NIST SRM 683 were intensively sampled by micro-drilling. Zinc isotope analyses for two nuggets show that they have δ66Zn of 0.14 ± 0.02‰ (2SD, N = 32) and 0.13 ± 0.02‰ (2SD, N = 33), respectively. These values are similar to those of two Zn metal nuggets (0.11 ± 0.02‰ vs. 0.12 ± 0.02‰) reported previously by Chen et al. (2016). We fully dissolved one nugget, producing pure Zn solution with identical Zn isotopic composition with the drilling samples. All results strongly support that NIST SRM 683 is homogeneous in Zn isotopic compositions which could be an ideal candidate for the next reference for Zn isotopes. Tests on more metal nuggets will be performed in a few months for further confirming the Zn isotope compositions and homogeneity. Reference: Albarède et al., 2004. 'The stable isotope geochemistry of copper and zinc', Reviews in Mineralogy and Geochemistry, 55: 409-27. Chen et al., 2016. 'Zinc Isotopic Compositions of NIST SRM 683 and Whole-Rock Reference Materials', Geostandards and Geoanalytical Research, 40: 417-32. Conway et al., 2013. 'A new method for precise determination of iron, zinc and cadmium stable isotope ratios in seawater by double-spike mass spectrometry', Analytica chimica acta, 793: 44-52. Moynier et al., 2017. 'The isotope geochemistry of zinc and copper', Reviews in Mineralogy and Geochemistry, 82: 543-600.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Conroy, Jessica L; Cobb, Kim M; Noone, David

The objective of this field campaign was to investigate climatic controls on the stable isotopic composition of water vapor, precipitation, and seawater in the western tropical Pacific. Simultaneous measurements of the stable isotopic composition of vapor and precipitation from April 28 to May 8, 2013, at the Manus Tropical Western Pacific Atmospheric Radiation Measurement site, provided several key insights into the nature of the climate signal archived in precipitation and vapor isotope ratios. We observed a large shift from lower to higher isotopic values in vapor and precipitation because of the passage of a mesoscale convective system west of themore » site and a transition from a regional stormy period into a more quiescent period. During the quiescent period, the stable isotopic composition of vapor and precipitation indicated the predominance of oceanic evaporation in determining the isotopic composition of boundary-layer vapor and local precipitation. There was not a consistent relationship between intra-event precipitation amount at the site and the stable isotopic composition of precipitation, thus challenging simplified assumptions about the isotopic “amount effect” in the tropics on the time scale of individual storms. However, some storms did show an amount effect, and deuterium excess values in precipitation had a significant relationship with several meteorological variables, including precipitation, temperature, relative humidity, and cloud base height across all measured storms. The direction of these relationships points to condensation controls on precipitation deuterium excess values on intra-event time scales. The relationship between simultaneous measurements of vapor and precipitation isotope ratios during precipitation events indicates the ratio of precipitation-to-vapor isotope ratios can diagnose precipitation originating from a vapor source unique from boundary-layer vapor and rain re-evaporation.« less

Origin of heavy Fe isotope compositions in high-silica igneous rocks: A rhyolite perspective

NASA Astrophysics Data System (ADS)

Du, De-Hong; Wang, Xiao-Lei; Yang, Tao; Chen, Xin; Li, Jun-Yong; Li, Weiqiang

2017-12-01

The origin of heavy Fe isotope compositions in high-silica (>70 wt% SiO2) igneous rocks remains a highly controversial topic. Considering that fluid exsolution in eruptive rocks is more straight-forward to constrain than in plutonic rocks, this study addresses the problem of Fe isotope fractionation in high-silica igneous rocks by measuring Fe isotope compositions of representative rhyolitic samples from the Neoproterozoic volcanic-sedimentary basins in southern China and the Triassic Tu Le Basin in northern Vietnam. The samples show remarkably varied δ56FeIRMM014 values ranging from 0.05 ± 0.05‰ to 0.55 ± 0.05‰, which is among the highest values reported from felsic rocks. The extensional tectonic setting and short melt residence time in magma chambers for the studied rhyolites rule out Soret diffusion and thermal migration processes as causes of the high δ56Fe values. Effects of volcanic degassing and fluid exsolution on bulk rock δ56Fe values for the rhyolites are also assessed using bulk rock geochemical indicators and Rayleigh fractionation models, and these processes are found to be insufficient to produce resolvable changes in Fe isotope compositions of the residual melt. The most probable mechanism accounting for heavy Fe isotope compositions in the high-silica rhyolites is narrowed down to fractional crystallization processes in the magma before rhyolite eruption. Removal of isotopically light Fe-bearing minerals (i.e. ulvöspinel-rich titanomagnetite, ilmenite and biotite) is proposed as the main cause of Fe isotope variation in silicic melts during magmatic evolution. This study implies that crystal fractionation is the dominant mechanism that controls Fe isotope fractionation in eruptive rocks and Fe isotopes could be used to study magmatic differentiation of high-silica magmas.

High-precision 87Sr/86Sr analyses in wines and their use as a geological fingerprint for tracing geographic provenance.

PubMed

Marchionni, Sara; Braschi, Eleonora; Tommasini, Simone; Bollati, Andrea; Cifelli, Francesca; Mulinacci, Nadia; Mattei, Massimo; Conticelli, Sandro

2013-07-17

The radiogenic isotopic compositions of inorganic heavy elements such as Sr, Nd, and Pb of the food chain may constitute a reliable geographic fingerprint, their isotopic ratios being inherited by the geological substratum of the territory of production. The Sr isotope composition of geomaterials (i.e., rocks and soils) is largely variable, and it depends upon the age of the rocks and their nature (e.g., genesis, composition). In this study we developed a high-precision analytical procedure for determining Sr isotopes in wines at comparable uncertainty levels of geological data. With the aim of verifying the possibility of using Sr isotope in wine as a reliable tracer for geographic provenance, we performed Sr isotope analyses of 45 bottled wines from four different geographical localities of the Italian peninsula. Their Sr isotope composition has been compared with that of rocks from the substrata (i.e., rocks) of their vineyards. In addition wines from the same winemaker but different vintage years have been analyzed to verify the constancy with time of the (87)Sr/(86)Sr. Sr isotope compositions have been determined by solid source thermal ionization mass spectrometry following purification of Sr in a clean laboratory. (87)Sr/(86)Sr of the analyzed wines is correlated with the isotopic values of the geological substratum of the vineyards, showing little or no variation within the same vineyard and among different vintages. Large (87)Sr/(86)Sr variation is observed among wines from the different geographical areas, reinforcing the link with the geological substratum of the production territory. This makes Sr isotopes a robust geochemical tool for tracing the geographic authenticity and provenance of wine.

Origin of the Lengshuigou porphyry-skarn Cu deposit in the Zha-Shan district, South Qinling, central China, and implications for differences between porphyry Cu and Mo deposits

NASA Astrophysics Data System (ADS)

Xie, Guiqing; Mao, Jingwen; Wang, Ruiting; Meng, Deming; Sun, Jia; Dai, Junzhi; Ren, Tao; Li, Jianbi; Zhao, Haijie

2017-04-01

Porphyry Cu and Mo deposits are two economically important types of metal deposits worldwide, but factors controlling their difference remain enigmatic. Compared with the well-studied large porphyry Mo province in the south margin of the North China Block (S-NCB), the origin of newly discovered porphyry Cu deposits in the South Qinling (SQB) is poorly constrained. Integrated zircon LA-ICPMS U-Pb and molybdenite Re-Os ages and geological evidence indicate three stages of magmatism at Lengshuigou: (1) late Neoproterozoic (718 to 704 Ma) quartz diorite + albitite + granite association during the pre-ore stage, (2) 146 to 145 Ma granodiorite porphyry during the syn-ore stage, and (3) 145 Ma granite porphyry during the post-ore stage. Elemental and Sr-Nd isotopic evidence provide important constraints on their magma source. Pre-ore Neoproterozoic quartz diorite + albitite + granite was derived by re-melting of a mixture of crustal and juvenile mantle materials, and stronger fractional crystallization was involved in these ore-hosting intrusions than in contemporary granitoids hosted in the Douling Group. Syn-ore granodiorite porphyry was derived from mantle-derived magma with contributions from different proportions of crustal components. Post-ore granite porphyry was derived mainly from a crustal source. Nearly contemporaneous porphyry Cu and Mo systems were identified in Qinling Province, including the 147-139 Ma porphyry Mo systems in the S-NCB and 150-146 Ma porphyry Cu systems in the SQB. Granitic stocks related to porphyry Cu systems in the SQB are characterized by moderate SiO2 contents (58.01-69.07 %) and less radiogenic Nd-Hf isotopes (ɛNd(t) = -3.8 to -6.3, ɛHf(t) = -4.5 to +1.6), whereas the granitic stocks related to porphyry Mo deposits in the S-NCB have high SiO2 concentrations (64.00-76.00 %) and more radiogenic Nd-Hf isotopes (ɛNd(t) = -18.0 to -11.6, ɛHf(t) = -26.3 to -13.5). In addition, molybdenite from the Chigou and Lengshuigou porphyry Cu deposits in the S-NCB show higher Re contents (77.50-394.3 ppm) than those from nearly contemporaneous porphyry Mo deposits (9.34-49.7 ppm) in the S-NCB. These lines of evidence indicate that a higher proportion of mantle component was involved in the formation of porphyry Cu deposits in the SQB than nearly contemporaneous porphyry Mo deposits in the S-NCB. It is most likely that the nature of the magma source plays an essential role in the differences between porphyry Cu and Mo deposits.

Understanding the Cu-Zn brass alloys using a short-range-order cluster model: significance of specific compositions of industrial alloys

PubMed Central

Hong, H. L.; Wang, Q.; Dong, C.; Liaw, Peter K.

2014-01-01

Metallic alloys show complex chemistries that are not yet understood so far. It has been widely accepted that behind the composition selection lies a short-range-order mechanism for solid solutions. The present paper addresses this fundamental question by examining the face-centered-cubic Cu-Zn α-brasses. A new structural approach, the cluster-plus-glue-atom model, is introduced, which suits specifically for the description of short-range-order structures in disordered systems. Two types of formulas are pointed out, [Zn-Cu12]Zn1~6 and [Zn-Cu12](Zn,Cu)6, which explain the α-brasses listed in the American Society for Testing and Materials (ASTM) specifications. In these formulas, the bracketed parts represent the 1st-neighbor cluster, and each cluster is matched with one to six 2nd-neighbor Zn atoms or with six mixed (Zn,Cu) atoms. Such a cluster-based formulism describes the 1st- and 2nd-neighbor local atomic units where the solute and solvent interactions are ideally satisfied. The Cu-Ni industrial alloys are also explained, thus proving the universality of the cluster-formula approach in understanding the alloy selections. The revelation of the composition formulas for the Cu-(Zn,Ni) industrial alloys points to the common existence of simple composition rules behind seemingly complex chemistries of industrial alloys, thus offering a fundamental and practical method towards composition interpretations of all kinds of alloys. PMID:25399835

Understanding the Cu-Zn brass alloys using a short-range-order cluster model: Significance of specific compositions of industrial alloys

DOE PAGES

Hong, H. L.; Wang, Q.; Dong, C.; ...

2014-11-17

Metallic alloys show complex chemistries that are not yet understood so far. It has been widely accepted that behind the composition selection lies a short-range-order mechanism for solid solutions. The present paper addresses this fundamental question by examining the face-centered-cubic Cu-Zn α-brasses. A new structural approach, the cluster-plus-glue-atom model, is introduced, which suits specifically for the description of short-range-order structures in disordered systems. Two types of formulas are pointed out, [Zn-Cu 12]Zn 1~6 and [Zn-Cu 12](Zn,Cu) 6, which explain the α-brasses listed in the American Society for Testing and Materials (ASTM) specifications. In these formulas, the bracketed parts represent themore » 1 st-neighbor cluster, and each cluster is matched with one to six 2 nd-neighbor Zn atoms or with six mixed (Zn,Cu) atoms. Such a cluster-based formulism describes the 1 st- and 2 nd-neighbor local atomic units where the solute and solvent interactions are ideally satisfied. The Cu-Ni industrial alloys are also explained, thus proving the universality of the cluster-formula approach in understanding the alloy selections. As a result, the revelation of the composition formulas for the Cu-(Zn,Ni) industrial alloys points to the common existence of simple composition rules behind seemingly complex chemistries of industrial alloys, thus offering a fundamental and practical method towards composition interpretations of all kinds of alloys.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Ching-Fong; Pokharel, Reeju; Brand, Michael J.

Here, we developed a copper/tungsten (Cu/W) composite for mesoscale Materials Science applications using the novel High-Energy Diffraction Microscopy (HEDM) technique. Argon-atomized copper powder was selected as the starting raw powder and screened to remove the extremely large particle fraction. Tungsten particles were collected by milling and screening the -325 mesh tungsten powder between 500 and 635 mesh sieves. Hot pressing of screened Cu powder was performed at 900 °C in Ar/4 %H 2 atmosphere. XRD and ICP results show that the hot-pressed Cu sample consists of about 5 vol% Cu 2O, which is caused by the presence of oxygen onmore » the surface of the starting Cu powder. Hot pressing the copper powder in a pure hydrogen atmosphere was successful in removing most of the surface oxygen. Our process was also implemented for hot pressing the Cu/W composite. The density of the Cu/W composites hot pressed at 950 °C in pure hydrogen was about 94 % of the theoretical density (TD). The hot-pressed Cu/W composites were further hot isostatic pressed at 1050 °C in argon atmosphere, which results in 99.6 % of the TD with the designed Cu grain size and W particle distribution. Tensile specimens with D-notch were machined using the wire EDM method. Furthermore, the processing and consolidation of these materials will be discussed in detail. The HEDM images are also showed and discussed.« less

Dielectric properties of (CuO, CaO2, and BaO)y/CuTl-1223 composites

NASA Astrophysics Data System (ADS)

Mumtaz, M.; Kamran, M.; Nadeem, K.; Jabbar, Abdul; Khan, Nawazish A.; Saleem, Abida; Tajammul Hussain, S.; Kamran, M.

2013-07-01

We synthesized (CuO, CaO2, and BaO)y/Cu0.5Tl0.5Ba2Ca2Cu3O10-δ (y = 0, 5%, 10%, 15%) composites by solid-state reaction and characterized them by x-ray diffraction, scanning electron microscopy, dc-resistivity, and Fourier transform infrared spectroscopy. Frequency and temperature dependent dielectric properties, such as real and imaginary parts of the dielectric constant, dielectric loss, and ac-conductivity of these composites were studied by capacitance and conductance measurements as a function of frequency (10 kHz to 10 MHz) and temperature (78 to 300 K). X-ray diffraction analysis reveals that the characteristic behavior of the superconductor phase and the structure of Cu0.5Tl0.5Ba2Ca2Cu3O10-δ are nearly undisturbed by doping with nanoparticles. Scanning electron microscopy images show the improvement in the intergranular linking between the superconducting grains occurring with increasing nanoparticle concentration. Microcracks are healed up with these nanoparticles, and superconducting volume fraction is also increased. Dielectric properties of these composites strongly depend on the frequency and temperature. Zero resistivity critical temperature and dielectric properties show opposite trends with the addition of nanoparticles to the Cu0.5Tl0.5Ba2Ca2Cu3O10-δ superconductor matrix.

Effect Of Substrates On The Fractionation Of Hydrogen Isotopes During Lipid-Biosynthesis By Haloarcula marismortui

NASA Astrophysics Data System (ADS)

Dirghangi, S. S.; Pagani, M.

2010-12-01

Lipids form an important class of proxies for paleoclimatological research, and hydrogen isotope ratios of lipids are being increasingly used for understanding changes in the hydrological system. Proper understanding of hydrogen isotope fractionation during lipid biosynthesis is therefore important and attention has been directed toward understanding the magnitude of hydrogen isotope fractionation that occurs during lipid biosynthesis in various organisms. Hydrogen isotope ratios of lipids depend on the hydrogen isotopic composition of the ambient water, hydrogen isotopic composition of NADPH used during biosynthesis, growth conditions, pathways of lipid biosynthesis, and substrates in the case of heterotrophic organisms. Recently it has been observed that NADPH contributes a significant part of the hydrogen in fatty acids synthesized by bacteria during heterotrophic growth (Zhang et al, 2009). As NADPH is formed by reduction of NADP+ during metabolism of substrates, different metabolic pathways form NADPH with different D/H ratios, which in turn results in variation in D/H ratios of lipids (Zhang et al, 2009). Therefore, substrates play a significant role in hydrogen isotopic compositions of lipids. For this study, we are investigating the effects of substrates on hydrogen isotope fractionation during biosynthesis of isoprenoidal lipids by heterotrophically growing halophilic archaea. Haloarcula marismortui is a halophilic archaea which synthesizes Archaeol (a diether lipid) and other isoprenoidal lipids. We have grown Haloarcula marismortui in pure cultures on three different substrates and are in the process of evaluating isotopic variability of Archaeol and other lipids associated with substrate and the D/H composition of ambient water. Our results will be helpful for a better understanding of hydrogen isotope fractionations during lipid synthesis by archaea. Also, halophilic archaea are the only source of archaeol in hypersaline environments. Therefore, our results will also indicate whether archaeol can be used as a proxy of ambient water hydrogen isotopic compositions in hypersaline environments.

A carbon isotope mass balance for an anoxic marine sediment: Isotopic signatures of diagenesis

NASA Technical Reports Server (NTRS)

Boehme, Susan E.

1993-01-01

A carbon isotope mass balance was determined for the sediments of Cape Lookout Bight, NC to constrain the carbon budgets published previously. The diffusive, ebullitive and burial fluxes of sigma CO2 and CH4, as well as the carbon isotope signatures of these fluxes, were measured. The flux-weighted isotopic signature of the remineralized carbon (-18.9 plus or minus 2.7 per mil) agreed with the isotopic composition of the remineralized organic carbon determined from the particulate organic carbon (POC) delta(C-13) profiles (-19.2 plus or minus 0.2), verifying the flux and isotopic signature estimates. The measured delta(C-13) values of the sigma CO2 and CH4 diffusive fluxes were significantly different from those calculated from porewater gradients. The differences appear to be influenced by methane oxidation at the sediment-water interface, although other potential processes cannot be excluded. The isotope mass balance provides important information concerning the locations of potential diagenetic isotope effects. Specifically, the absence of downcore change in the delta(C-13) value of the POC fraction and the identical isotopic composition of the POC and the products of remineralization indicate that no isotopic fractionation is expressed during the initial breakdown of the POC, despite its isotopically heterogeneous composition.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Polat, B. D.; Eryilmaz, O. L.; Keles, O

Compositionally graded and non-graded composite SiCu thin films were deposited by magnetron sputtering technique on Cu disks for investigation of their potentials in lithium ion battery applications. The compositionally graded thin film electrodes with 30 at.% Cu delivered a 1400 mAh g-1 capacity with 80% Coulombic efficiency in the first cycle and still retained its capacity at around 600 mAh g-1 (with 99.9% Coulombic efficiency) even after 100 cycles. On the other hand, the non-graded thin film electrodes with 30 at.% Cu exhibited 1100 mAh g-1 as the first discharge capacity with 78% Coulombic efficiency but the cycle life ofmore » this film degraded very quickly, delivering only 250 mAh g-1 capacity after 100th cycles. Not only the Cu content but also the graded film thickness were believed to be the main contributors to the much superior performance of the compositionally graded SiCu films. We also believe that the Cu-rich region of the graded film helped reduce internal stress build-up and thus prevented film delamination during cycling. In particular, the decrease of Cu content from interface region to the top of the coating reduced the possibility of stress build-up across the film during cycling, thus leading to a high electrochemical performance.« less

Spacecraft measurements of the elemental and isotopic composition of solar energetic particles

NASA Technical Reports Server (NTRS)

Mewaldt, R. A.

1980-01-01

Within the past few years, instruments flown on satellites and space probes have made significant progress in measuring the elemental and isotopic composition of energetic heavy nuclei accelerated in solar flares. These new observations are discussed, focusing on: (1) the energy dependence of the elemental composition at energies not greater than 1 MeV/nucleon; (2) flare to flare variations in the composition; and (3) comparisons of the average solar particle abundances (Z not less than 2 and not greater than 28) with other measures of the solar composition, including photospheric, coronal, and solar wind observations. These comparisons have led to the suggestion that solar flares sample the composition of the corona. Isotopic measurements of heavy solar flare nuclei have recently added a new dimension to these studies. In particular, the isotopic composition of solar flare neon has been found to be significantly different from that measured in the solar wind, but consistent with the meteoritic component neon-A.

Origin of petroporphyrins. 2. Evidence from stable carbon isotopes

NASA Technical Reports Server (NTRS)

Boreham, C. J.; Fookes, C. J.; Popp, B. N.; Hayes, J. M.

1990-01-01

Compared with the carbon-13 isotopic composition of the ubiquitous C32DPEP (DPEP, deoxophylloerythroetioporphyrin) the heavy but equivalent carbon-13 isotopic composition for the porphyrin structures 15(2)-methyl-15,17-ethano-17-nor-H-C30DPEP and 15,17-butano-, 13,15-ethano-13(2),17-propano-, and 13(1)-methyl-13,15-ethano-13(2),17-propanoporphyrin suggests a common precursor, presumably chlorophyll c, for these petroporphyrins isolated from the marine Julia Creek oil shale and the lacustrine Condor oil shale. Similarly, the heavy but variable carbon-13 isotopic composition of 7-nor-H-C31DPEP compared with C32DPEP is consistent with an origin from both chlorophyll b and chlorophyll c3. The equivalent carbon-13 isotopic composition for 13(2)-methyl-C33DPEP compared with C32DPEP suggests a common origin resulting from a weighted average of chlorophyll inputs.

New technique for study on isotopic fractionation between sea water and foraminiferal growing processes

NASA Astrophysics Data System (ADS)

Cang, Shuxi; Shackleton, N. J.

1990-12-01

The stable isotopic δ18O and δ13C composition of foraminiferal shell calcite varies as a function of many factors including temperature and salinity. In order to understand and interpret the variations in the isotopic composition of foraminiferal shell calcite, research has been recently focused on the role of the “vital effects”. Our examination of the lamella structure of several recent planktonic foraminifera indicates that the secretion of sequential lamellae results in multiple lamillae on earlier chambers and a single lamella on the final chamber. We used a very simple procedure to separate the individual whole test of foraminifera into several chambers and measured the isotopic composition of each growth stage chamber. The results indicate that the stable isotopic composition (carbon and oxygen), particularly that of the last two chambers, of the foraminiferal test varies as a function of the individual growing process.

Hafnium isotope stratigraphy of ferromanganese crusts

PubMed

Lee; Halliday; Hein; Burton; Christensen; Gunther

1999-08-13

A Cenozoic record of hafnium isotopic compositions of central Pacific deep water has been obtained from two ferromanganese crusts. The crusts are separated by more than 3000 kilometers but display similar secular variations. Significant fluctuations in hafnium isotopic composition occurred in the Eocene and Oligocene, possibly related to direct advection from the Indian and Atlantic oceans. Hafnium isotopic compositions have remained approximately uniform for the past 20 million years, probably reflecting increased isolation of the central Pacific. The mechanisms responsible for the increase in (87)Sr/(86)Sr in seawater through the Cenozoic apparently had no effect on central Pacific deep-water hafnium.

A Sr and Mg isotopic study of soil and stream waters along an erosional gradient, Sierra Nevada, California

NASA Astrophysics Data System (ADS)

Rosen, V. B.; Maher, K.; Kouba, C. M.; Weinman, B. A.; Yoo, K.; Mudd, S. M.

2012-12-01

Since chemical weathering rates are proposed to regulate atmospheric CO2 concentrations and by extension global temperature over geologic timescales, understanding the relationship between chemical weathering rates and physical erosion is crucial to accurately interpreting Earth's climate history. The rate of supply of fresh minerals to the weathering zone is known to be an important control on chemical weathering rates. However, the consequences of physical erosion on the isotopic composition of weathering-derived solutes are more difficult to assess. This study capitalizes on a series of granitic hillslope transects with different erosion rates but similar climate, vegetation, and bedrock, in order to assess the consequences of erosion on the Sr and Mg isotopic composition of solutes. Reactive transport model simulations of varying complexity have been used to complement the field measurements and to analyze the sensitivity of fluid isotopic compositions to changes in key parameters such as erosion rate, flow rate, and biological cycling. The three hillslopes in the Feather River Basin, California reflect different degrees of channel erosion at their bases—BRC is a hillslope with active channel incision (60% average slope, below the knickpoint), FTA is a hillslope reflecting the transition between the relict and modern-day incising areas (50% average slope, at the knickpoint), and POMD is a 30% average hillslope in the relict landscape above the knickpoint. We measured the major element compositions, as well as the Sr and Mg isotopic compositions of soil water leaches (deionized water leaches), lysimeters, stream waters, and groundwaters by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The 87Sr/86Sr values of soil and stream waters show minimal variation (0.7042 to 0.7046) as a function of soil depth, erosion rate, or sampling season despite abundant radiogenic biotite in the profiles. These results agree with the reactive transport model predictions at high erosion rates, and suggest that soil residence times and isotopic equilibrium times are too short for biotite weathering to influence the solute isotopic composition. In contrast, model results for δ26Mg of the soil waters and minerals suggest that the Mg isotopic composition of the solute changes as a function of erosion rate because of shorter isotopic equilibrium length scales at higher erosion rates. The isotopic reactive transport modeling, combined with hillslope depth profiles and stream water analyses, provides a useful approach for linking the isotopic composition of solutes to erosion rates. This study may provide insights into past and present riverine isotopic compositions, and contribute to our understanding of how surface processes have influenced past atmospheric conditions.

Importance of depth and intensity of convection on the isotopic composition of water vapor as seen from IASI and TES δD observations

NASA Astrophysics Data System (ADS)

Lacour, Jean-Lionel; Risi, Camille; Worden, John; Clerbaux, Cathy; Coheur, Pierre-François

2018-01-01

We use tropical observations of the water vapor isotopic composition, derived from IASI and TES spaceborne measurements, to show that the isotopic composition of water vapor in the free troposphere is sensitive to both the depth and the intensity of convection. We find that for any given precipitation intensity, vapor associated with deep convection is isotopically depleted relative to vapor associated with shallow convection. The intensity of precipitation also plays a role as for any given depth of convection, the relative enrichment of water vapor decreases as the intensity of precipitation increases. Shallow convection, via the uplifting of enriched boundary layer air into the free troposphere and the convective detrainment, enriches the free troposphere. In contrast, deep convection is associated with processes that deplete the water vapor in the free troposphere, such as rain re-evaporation. The results of this study allow for a better identification of the parameters controlling the isotopic composition of the free troposphere and indicate that the isotopic composition of water vapor can be used to evaluate the relative contributions of shallow and deep convection in global models.

Magnesium isotope evidence that accretional vapour loss shapes planetary compositions

PubMed Central

Hin, Remco C.; Coath, Christopher D.; Carter, Philip J.; Nimmo, Francis; Lai, Yi-Jen; Pogge von Strandmann, Philip A.E.; Willbold, Matthias; Leinhardt, Zoë M.; Walter, Michael J.; Elliott, Tim

2017-01-01

It has long been recognised that Earth and other differentiated planetary bodies are chemically fractionated compared to primitive, chondritic meteorites and by inference the primordial disk from which they formed. An important question has been whether the notable volatile depletions of planetary bodies are a consequence of accretion1, or inherited from prior nebular fractionation2. The isotopic compositions of the main constituents of planetary bodies can contribute to this debate3–6. Using a new analytical approach to address key issues of accuracy inherent in conventional methods, we show that all differentiated bodies have isotopically heavier magnesium compositions than chondritic meteorites. We argue that possible magnesium isotope fractionation during condensation of the solar nebula, core formation and silicate differentiation cannot explain these observations. However, isotopic fractionation between liquid and vapour followed by vapour escape during accretionary growth of planetesimals generates appropriate residual compositions. Our modelling implies that the isotopic compositions of Mg, Si and Fe and the relative abundances of the major elements of Earth, and other planetary bodies, are a natural consequence of substantial (~40% by mass) vapour loss from growing planetesimals by this mechanism. PMID:28959965

Spatial patterns of throughfall isotopic composition at the event and seasonal timescales

NASA Astrophysics Data System (ADS)

Allen, Scott T.; Keim, Richard F.; McDonnell, Jeffrey J.

2015-03-01

Spatial variability of throughfall isotopic composition in forests is indicative of complex processes occurring in the canopy and remains insufficiently understood to properly characterize precipitation inputs to the catchment water balance. Here we investigate variability of throughfall isotopic composition with the objectives: (1) to quantify the spatial variability in event-scale samples, (2) to determine if there are persistent controls over the variability and how these affect variability of seasonally accumulated throughfall, and (3) to analyze the distribution of measured throughfall isotopic composition associated with varying sampling regimes. We measured throughfall over two, three-month periods in western Oregon, USA under a Douglas-fir canopy. The mean spatial range of δ18O for each event was 1.6‰ and 1.2‰ through Fall 2009 (11 events) and Spring 2010 (7 events), respectively. However, the spatial pattern of isotopic composition was not temporally stable causing season-total throughfall to be less variable than event throughfall (1.0‰; range of cumulative δ18O for Fall 2009). Isotopic composition was not spatially autocorrelated and not explained by location relative to tree stems. Sampling error analysis for both field measurements and Monte-Carlo simulated datasets representing different sampling schemes revealed the standard deviation of differences from the true mean as high as 0.45‰ (δ18O) and 1.29‰ (d-excess). The magnitude of this isotopic variation suggests that small sample sizes are a source of substantial experimental error.

What controls silicon isotope fractionation during dissolution of diatom opal?

NASA Astrophysics Data System (ADS)

Wetzel, F.; de Souza, G. F.; Reynolds, B. C.

2014-04-01

The silicon isotope composition of opal frustules from photosynthesising diatoms is a promising tool for studying past changes in the marine silicon cycle, and indirectly that of carbon. Dissolution of this opal may be accompanied by silicon isotope fractionation that could disturb the pristine silicon isotope composition of diatom opal acquired in the surface ocean. It has previously been shown that dissolution of fresh and sediment trap diatom opal in seawater does fractionate silicon isotopes. However, as the mechanism of silicon isotope fractionation remained elusive, it is uncertain whether opal dissolution in general is associated with silicon isotope fractionation considering that opal chemistry and surface properties are spatially and temporally (i.e. opal of different age) diverse. In this study we dissolved sediment core diatom opal in 5 mM NaOH and found that this process is not associated with significant silicon isotope fractionation. Since no variability of the isotope effect was observed over a wide range of dissolution rates, we can rule out the suggestion that back-reactions had a significant influence on the net isotope effect. Similarly, we did not observe an impact of temperature, specific surface area, or degree of undersaturation on silicon isotope partitioning during dissolution, such that these can most likely also be ruled out as controlling factors. We discuss the potential impacts of the chemical composition of the dissolution medium and age of diatom opal on silicon isotope fractionation during dissolution. It appears most likely that the controlling mechanism of silicon isotope fractionation during dissolution is related to the reactivity, or potentially, aluminium content of the opal. Such a dependency would imply that silicon isotope fractionation during dissolution of diatom opal is spatially and temporally variable. However, since the isotope effects during dissolution are small, the silicon isotope composition of diatom opal appears to be robust against dissolution in the deep sea sedimentary environment.

Characteristics of Martian Crustal Materials and Implications for Magmatic Assimilation: Preliminary Re-Os Isotope and Highly Siderophile Element Abundance Data for Nakhlites and Tissint

NASA Astrophysics Data System (ADS)

Mari, N.; Riches, A. J. V.; Hallis, L. J.; Lee, M. R.

2017-07-01

This project, for the first time, aims to integrate nakhlite Os-isotope compositions and HSE abundance data with S-isotope compositions for sample fractions for which textural information is constrained prior to destructive analyses.

Isotopic Composition of Barium in Single Presolar Silicon Carbide Grains

NASA Technical Reports Server (NTRS)

Savina, M. R.; Tripa, C. E.; Pellin, M. J.; Davis, A. M.; Clayton, R. N.; Lewis, R. S.; Amari, S.

2002-01-01

We have measured Ba isotope distributions in individual presolar SiC grains. We find that the Ba isotopic composition in mainstream SiC grains is consistent with models of nucleosynthesis in low to intermediate mass asymptotic giant branch (AGB) stars. Additional information is contained in the original extended abstract.

Soil drying effects on the carbon isotope composition of soil respiration

EPA Science Inventory

Stable isotopes are used widely as a tool for determining sources of carbon (C) fluxes in ecosystem C studies. Environmental factors that change over time, such as moisture, can create dynamic changes in the isotopic composition of C assimilated by plants, and offers a unique opp...

Annealing effect on thermal conductivity and microhardness of carbon nanotube containing Se80Te16Cu4 glassy composites

NASA Astrophysics Data System (ADS)

Upadhyay, A. N.; Tiwari, R. S.; Singh, Kedar

2018-02-01

This study deals with the effect of thermal annealing on structural/microstructural, thermal and mechanical behavior of pristine Se80Te16Cu4 and carbon nanotubes (CNTs) containing Se80Te16Cu4 glassy composites. Pristine Se80Te16Cu4, 3 and 5 wt%CNTs-Se80Te16Cu4 glassy composites are annealed in the vicinity of glass transition temperature to onset crystallization temperature (340-380 K). X-ray diffraction (XRD) pattern revealed formation of polycrystalline phases of hexagonal CuSe and trigonal selenium. The indexed d-values in XRD patterns are in well conformity with the d-values obtained after the indexing of the ring pattern of selected area electron diffraction pattern of TEM images. The SEM investigation exhibited that the grain size of the CNTs containing Se80Te16Cu4 glassy composites increased with increasing annealing temperature and decreased at further higher annealing temperature. Thermal conductivity, microhardness exhibited a substantial increase with increasing annealing temperature of 340-360 K and slightly decreases for 380 K. The variation of thermal conductivity and microhardness can be explained by cross-linking formation and voids reduction.

Isotopic anomalies - Chemical memory of Galactic evolution

NASA Technical Reports Server (NTRS)

Clayton, Donald D.

1988-01-01

New mechanisms for the chemical memory of isotopic anomalies are proposed which are based on the temporal change during the chemical evolution of the Galaxy of the isotopic composition of the mean ejecta from stars. Because of the differing temporal evolution of primary and secondary products of nucleosynthesis, the isotopic composition of the bulk interstellar medium changes approximately linearly with time, and thus any dust component having an age different from that of average dust will be isotopically anomalous. Special attention is given to C, O, Mg, Si, and isotopically heavy average-stellar condensates of SiC.

Using elemental profiles and stable isotopes to trace the origin of green coffee beans on the global market.

PubMed

Santato, Alessandro; Bertoldi, Daniela; Perini, Matteo; Camin, Federica; Larcher, Roberto

2012-09-01

A broad elemental profile incorporating 54 elements (Li, Be, B, Na, Mg, Al, P, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Mo, Pd, Ag, Cd, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Tm, Yb, Re, Ir, Pt, Au, Hg, Tl, Pb, Bi and U) in combination with δ(2) H, δ(13) C, δ(15) N and δ(18) O was used to characterise the composition of 62 green arabica (Coffea arabica) and robusta (Coffea canephora) coffee beans grown in South and Central America, Africa and Asia, the four most internationally renowned areas of production. The δ(2) H, Mg, Fe, Co and Ni content made it possible to correctly assign 95% of green coffee beans to the appropriate variety. Canonical discriminant analysis, performed using δ(13) C, δ(15) N, δ(18) O, Li, Mg, P, K, Mn, Co, Cu, Se, Y, Mo, Cd, La and Ce correctly traced the origin of 98% of coffee beans. Copyright © 2012 John Wiley & Sons, Ltd.

Facile synthesis of Cu/Cu{sub x}O nanoarchitectures with adjustable phase composition for effective NO{sub x} gas sensor at room temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Lixue; Li, Li; Yang, Ying

2013-10-15

Graphical abstract: The Cu/Cu{sub x}O nanoarchitectures with 30–70 nm hollow nanospheres reduced by 3 mmol NaBH{sub 4} exhibits excellent gas-sensing property to low-concentration NO{sub x} gas at room temperature. - Highlights: • The Cu/Cu{sub x}O nanoarchitectures with hollow nanospheres are successfully synthesized. • The method is used for preparing the with Cu/Cu{sub x}O adjustable phase composition. • The C3 sample exhibites excellent gas-sensing propertie to NO{sub x} at room temperation. • The Cu/Cu{sub x}O nanoarchitectures have significant for application of gas sensor. - Abstract: The Cu/Cu{sub x}O nanoarchitectures with 30–70 nm hollow nanospheres are successfully synthesized by a facile wetmore » chemical method. The synthesized products have been studied by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and thermo gravimetric-differential scanning calorimetry (TG-DSC) analysis. The Cu/Cu{sub x}O sensors based on the nanoarchitectures are used to detect the NO{sub x} at room temperature. The results demonstrate that the obtained Cu/Cu{sub x}O nanoarchitectures reduced by 3 mmol NaBH{sub 4} exhibits excellent gas-sensing properties: low detection limit of 0.97 ppm, relatively high sensitivity, short response time, broad linear range and high selectivity. The reasons for gas-sensing activity enhancement on Cu/Cu{sub x}O nanoarchitectures are discussed. The Cu/Cu{sub x}O nanocrystalline with the hierarchical pores structure and tunable compositions have significant for application of gas sensor.« less

The Effect of Palladium Additions on the Solidus/Liquidus Temperatures and Wetting Properties of Ag-CuO Based Air Brazes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Darsell, Jens T.; Weil, K. Scott

2007-05-16

As a means of increasing the use temperature of ceramic-ceramic and ceramic-metal air brazes, palladium was investigated as possible ternary addition to the currently employed silver - copper oxide system. The silver component was directly substituted with palladium to form the following series of alloys: (100-y)[(100-z)Pd - (z)Ag] - (y)CuOx where y = 0 - 34 mol% CuOx, z = 50 - 100 mol% silver, and x = 0, 0.5, and 1, denoting copper metal, Cu2O, or CuO. From differential scanning calorimetry, it was determined that the addition of palladium causes an increase in the solidus and liquidus temperatures ofmore » the resulting Pd-Ag-CuO brazes. In general, the liquidus was found to increase by approximately 220°C for the (100-y)(25Pd - 75Ag) - (z)CuOx filler metal compositions relative to comparable Ag-CuOx alloys. Likewise, the solidus was found to increase for these alloys, respectively by 185°C and 60°C, respectively for CuOx contents of y = 0 - 1mol% and 4 - 10 mol%. For the (100-y)(50Pd - 50Ag) - (y)CuOx alloys, the solidus increased between 280 - 390°C over a copper oxide compositional range of x = 0 to 8 mol%. It was determined from sessile drop experiments conducted on alumina substrates that in all cases the palladium causes an increase in the wetting angle relative to the corresponding binary braze. Alloy compositions of (100-y)(25Pd - 75Ag) - (y)CuOx displayed increased wetting angles of 5-20° relative to comparable binary compositions. (100-y)(50Pd - 50Ag) - (y)CuOx alloys exhibited an increase in contact angle of 10-60° and compositions containing less than 10 mol% CuOx were not able to wet the substrate. Scanning electron microscopy indicated that the microstructure of the braze consists of discrete CuOx precipitates in an alloyed silver-palladium matrix. In both the binary and ternary filler metal formulations, a reaction layer consisting of CuAlO2 was observed along the interface with the alumina substrate. This reaction product appears to be beneficial in promoting wetting by the remaining braze filler metal. However the formation of this layer is hindered as the concentration of palladium in the filler metal is increased, which appears to be the primary cause of poor wettability in these compositions, as indicated by the substantial amount of porosity found along the braze/substrate interface.« less