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.

Zinc isotope anomalies. [in Allende meteorite

NASA Technical Reports Server (NTRS)

Volkening, J.; Papanastassiou, D. A.

1990-01-01

The Zn isotope composition in refractory-element-rich inclusions of the Allende meteorite are determined. Typical inclusions contain normal Zn. A unique inclusion of the Allende meteorite shows an excess for Zn-66 of 16.7 + or - 3.7 eu (1 eu = 0.01 percent) and a deficit for Zn-70 of 21 + or - 13 eu. These results indicate the preservation of exotic components even for volatile elements in this inclusion. The observed excess Zn-66 correlates with excesses for the neutron-rich isotopes of Ca-48, Ti-50, Cr-54, and Fe-58 in the same inclusion.

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.

Silicon and Zinc Isotopes in Ocean Island Basalts

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Savage, P. S.; Jackson, M. G.; Moreira, M. A.; Day, J. M.; Moynier, F.

2013-12-01

Analyses of Ocean Island Basalts (OIB) have shown that the Earth's mantle contains isotopically distinct components, but current debate about the degree and scale of compositional variability persists. Isotopic heterogeneities in OIB for both radiogenic (e.g. Sr, Nd, Pb) and stable (e.g. Li, O, Ca) isotope systems have been attributed to the presence of recycled materials in different mantle reservoirs [1]. The study of both silicon and zinc isotopes in OIB form a complimentary approach to investigate potential heterogeneities in the mantle. Both isotope systems show limited fractionation during igneous process [2,3]. However, both Si and Zn exhibit larger (>1‰) variability in low-temperature environments (e.g. as a result of chemical weathering and biological utilization). Therefore, Si and Zn isotopes may be useful as tracers for the presence of crustal material (derived from low-T surface processes) in OIB source regions. Furthermore, characterizing the isotopic composition of the mantle is of central importance to the use of these isotopic systems as a basis for interplanetary comparisons. Here we present high-precision Si and Zn isotopic data obtained by MC-ICPMS for a diverse suite of OIB representing the EM-1, EM-2, and HIMU mantle components. Samples represent locations in the Pacific, Atlantic, and Indian Oceans. Data are reported as the permil deviation (×2 sd) from NBS28 for Si (δ30Si) and JMC-Lyon for Zn (δ66Zn). Average δ30Si values for OIB from EM-1 (-0.32×0.09‰), EM-2 (-0.30×0.03‰), and HIMU (-0.34×0.12‰) are all in general agreement with previous estimates for the δ30Si value of Bulk Silicate Earth (BSE) [4]. Similarly, the δ66Zn average values for OIB from the EM-1, EM-2, and HIMU components (0.31×0.06‰, 0.31×0.04‰, 0.31×0.05‰, respectively) agree well with previously published data for the δ66Zn value of BSE [3]. At the current levels of precision, both Si and Zn isotopes exhibit little variation in OIB, confirming the large-scale homogeneity of the mantle for these isotopic systems. Furthermore, when averaged according to surface location, neither Si nor Zn shows any variation in isotopic composition according to oceanic basin. However, some small variations in the data may be present; many HIMU samples (Mangaia, Cape Verde) are enriched in the lighter isotopes of Si (δ30Si tending toward chondritic values), which might reflect preservation of isotopic heterogeneity within the mantle, an incorporation of an isotopically light component in the source of these lavas, or isotopic fractionation during magmatic differentiation. References: [1] Hofmann, RiMG 2007 [2] Savage et al., GCA 2011 [3] Chen et al., EPSL 2013 [4] Savage et al., EPSL 2010

Cu-Zn isotope constraints on the provenance of air pollution in Central Europe: Using soluble and insoluble particles in snow and rime.

PubMed

Novak, Martin; Sipkova, Adela; Chrastny, Vladislav; Stepanova, Marketa; Voldrichova, Petra; Veselovsky, Frantisek; Prechova, Eva; Blaha, Vladimir; Curik, Jan; Farkas, Juraj; Erbanova, Lucie; Bohdalkova, Leona; Pasava, Jan; Mikova, Jitka; Komarek, Arnost; Krachler, Michael

2016-11-01

Copper (Cu) and zinc (Zn) isotope ratios can be used to fingerprint sources and dispersion pathways of pollutants in the environment. Little is known, however, about the potential of δ 65 Cu and δ 66 Zn values in liquid and solid forms of atmospheric deposition to distinguish between geogenic, industrial, local and remote sources of these potentially toxic base metals. Here we present Cu-Zn deposition fluxes at 10 mountain-top sites in the Czech Republic, a region affected by extremely high industrial emission rates 25 years ago. Additionally, we monitored isotope composition of Cu and Zn in vertical and horizontal atmospheric deposition at two sites. We compared δ 65 Cu and δ 66 Zn values in snow and rime, extracted by diluted HNO 3 and concentrated HF. Cu and Zn isotope signatures of industrial pollution sources were also determined. Cu and Zn deposition fluxes at all study sites were minute. The mean δ 65 Cu value of atmospheric deposition (-0.07‰) was higher than the mean δ 65 Cu value of pollution sources (-1.17‰). The variability in δ 65 Cu values of atmospheric deposition was lower, compared to the pollution sources. The mean δ 66 Zn value of atmospheric deposition (-0.09‰) was slightly higher than the mean δ 66 Zn value of pollution sources (-0.23‰). The variability in δ 66 Zn values of atmospheric deposition was indistinguishable from that of pollution sources. The largest isotope differences (0.35‰) were observed between the insoluble and soluble fractions of atmospheric deposition. These differences may result from different sources of Cu/Zn for each fraction. The difference in isotope composition of soluble and insoluble particles appears to be a promising tool for pollution provenance studies in Central Europe. Copyright © 2016 Elsevier Ltd. All rights reserved.

The role of soil biogeochemistry in wine taste: Soil factors influencing grape elemental composition, photosynthetic biomarkers and Cu/Zn isotopic signature of Vitis vinifera

NASA Astrophysics Data System (ADS)

Blotevogel, Simon; Oliva, Priscia; Darrozes, José; Viers, Jérôme; Audry, Stéphane; Courjault-Radé, Pierre; Orgogozo, Laurent; Le Guedard, Marina; Schreck, Eva

2015-04-01

Understanding the influence of soil composition in wine taste is of great economic and environmental interest in France and around the world. Nevertheless the impact of soil composition on wine taste is still controversially discussed. Since inorganic soil components do not have a proper taste and do not enter the plant anyway, their influence needs to be induced by nutrient absorption and its impact on plant functioning and grape composition. Indeed recent development of geological tracers of origin proof the existence of soil chemical and isotopic signatures in wine. However, type and scale of the impact of soil composition on wine taste are not well understood yet, and little experimental evidence exists due to the complexity of mechanisms involved. Thus, to provide evidence for the impact of soil composition on grape composition and potentially wine taste, we studied soil and plant material from two relevant vineyards (Soave, Italia). On those two directly adjacent vineyards, two different wines are produced with the same plant material and cultivation techniques. The vineyards only differ by their underlying bedrock - limestone versus basaltic rock - and thus present suitable conditions for investigating the impact of soil composition on grapes and wine. Pedological and mineralogical parameters were analyzed for the two vineyards whereas chemical extractions (citrate, CaCl2) were performed to determine nutrient bioavailability in both soils. Elemental compositions were determined by ICP-MS analyses in different compartments (soils, vine leaves and grapes). Isotopic fractionation of Cu and Zn was investigated in various samples as source tracers and in order to better understand fractionation mechanisms involved. Finally, plant health was studied using the Omega-3 biomarker which determines the fatty acid composition in vine leaves, directly involved in photosynthetic processes. Results show that the vineyards are characterized by two different soil types due to the geological difference. These soils differ in elemental compositions and bioavailability of mineral nutrients, preconditions for a potential influence on plants and wine. Elemental ratios of soils are partly transmitted to leaves and grapes of correspondent plants, including nutrients such as Ca. Plant photosynthetic functioning is significantly better on the limestone vineyard due to lower Cu bioavailability: Omega-3 values are negatively linked to Cu bioavailability in corresponding soils. These observations suggest a difference in organic molecule synthesis depending on the vineyard soil, which might include components relevant for taste and fermentation. Cu and Zn isotopic ratios do not differ between both soils. The main fractionation of Cu and Zn isotopes occurs at the soil-plant interface making those isotopes suitable tracers for uptake mechanisms. As a result Zn isotope ratios reveal a strong recycling of Zn in the soil-plant continuum. Our results show a significant influence of soil composition on grape composition, plant biochemistry and potentially wine taste. Determination of organic and sensorial composition of grapes and wine is ongoing and will be discussed in further communications.

Nickel and zinc isotope fractionation in hyperaccumulating and nonaccumulating plants.

PubMed

Deng, Teng-Hao-Bo; Cloquet, Christophe; Tang, Ye-Tao; Sterckeman, Thibault; Echevarria, Guillaume; Estrade, Nicolas; Morel, Jean-Louis; Qiu, Rong-Liang

2014-10-21

Until now, there has been little data on the isotope fractionation of nickel (Ni) in higher plants and how this can be affected by plant Ni and zinc (Zn) homeostasis. A hydroponic cultivation was conducted to investigate the isotope fractionation of Ni and Zn during plant uptake and translocation processes. The nonaccumulator Thlaspi arvense, the Ni hyperaccumulator Alyssum murale and the Ni and Zn hyperaccumulator Noccaea caerulescens were grown in low (2 μM) and high (50 μM) Ni and Zn solutions. Results showed that plants were inclined to absorb light Ni isotopes, presumably due to the functioning of low-affinity transport systems across root cell membrane. The Ni isotope fractionation between plant and solution was greater in the hyperaccumulators grown in low Zn treatments (Δ(60)Ni(plant-solution) = -0.90 to -0.63‰) than that in the nonaccumulator T. arvense (Δ(60)Ni(plant-solution) = -0.21‰), thus indicating a greater permeability of the low-affinity transport system in hyperaccumulators. Light isotope enrichment of Zn was observed in most of the plants (Δ(66)Zn(plant-solution) = -0.23 to -0.10‰), but to a lesser extent than for Ni. The rapid uptake of Zn on the root surfaces caused concentration gradients, which induced ion diffusion in the rhizosphere and could result in light Zn isotope enrichment in the hyperaccumulator N. caerulescens. In high Zn treatment, Zn could compete with Ni during the uptake process, which reduced Ni concentration in plants and decreased the extent of Ni isotope fractionation (Δ(60)Ni(plant-solution) = -0.11 to -0.07‰), indicating that plants might take up Ni through a low-affinity transport system of Zn. We propose that isotope composition analysis for transition elements could become an empirical tool to study plant physiological processes.

Zinc isotope anomalies in Allende meteorite inclusions

NASA Technical Reports Server (NTRS)

Loss, R. D.; Lugmair, G. W.

1990-01-01

The isotopic compositions of Zn, Cr, Ti, and Ca have been measured in a number of CAIs from the Allende meteorite. The aim was to test astrophysical models which predict large excesses of Zn-66 to accompany excesses in the neutron-rich isotopes of Ca, Ti, Cr, and Ni. Some of the CAIs show clearly resolved but small excesses for Zn-66 which are at least an order of magnitude smaller than predicted. This result may simply reflect the volatility and chemical behavior of Zn as compared to the other (more refractory) anomalous elements found in these samples. Alternatively, revision of parameters and assumptions used for the model calculations may be required.

A critical examination of the possible application of zinc stable isotope ratios in bivalve mollusks and suspended particulate matter to trace zinc pollution in a tropical estuary.

PubMed

Araújo, Daniel; Machado, Wilson; Weiss, Dominik; Mulholland, Daniel S; Boaventura, Geraldo R; Viers, Jerome; Garnier, Jeremie; Dantas, Elton L; Babinski, Marly

2017-07-01

The application of zinc (Zn) isotopes in bivalve tissues to identify zinc sources in estuaries was critically assessed. We determined the zinc isotope composition of mollusks (Crassostrea brasiliana and Perna perna) and suspended particulate matter (SPM) in a tropical estuary (Sepetiba Bay, Brazil) historically impacted by metallurgical activities. The zinc isotope systematics of the SPM was in line with mixing of zinc derived from fluvial material and from metallurgical activities. In contrast, source mixing alone cannot account for the isotope ratios observed in the bivalves, which are significantly lighter in the contaminated metallurgical zone (δ 66 Zn JMC  = +0.49 ± 0.06‰, 2σ, n = 3) compared to sampling locations outside (δ 66 Zn JMC  = +0.83 ± 0.10‰, 2σ, n = 22). This observation suggests that additional factors such as speciation, bioavailability and bioaccumulation pathways (via solution or particulate matter) influence the zinc isotope composition of bivalves. Copyright © 2017 Elsevier Ltd. All rights reserved.

Cadmium and zinc isotopes of organic-rich marine sediments during Oceanic Anoxic Event 2

NASA Astrophysics Data System (ADS)

Sweere, T.; Dickson, A. J.; Jenkyns, H. C.; Porcelli, D.; Henderson, G. M.; van den Boorn, S.

2017-12-01

Mesozoic Oceanic Anoxic Events (OAEs) are characterized by widespread deposition of organic-rich sediments and the spread of low-oxygen marine environments. To drive and sustain unusually efficient carbon-burial during these events requires high export productivity rates, which has to be supported by an abundance of nutrients in the surface ocean. The presence of redox-sensitive bio-essential micronutrients may be particularly important, and potentially bio-limiting, during such events as they may be drawn down into sediment under low-oxygen conditions. Cadmium and zinc isotopes have potential as tracers for past (micro)nutrient dynamics considering their nutrient-like distribution in the modern ocean and isotope fractionation with uptake by primary producers. The modern deep ocean is generally well mixed for Cd and Zn while short-term cycling of these elements in the surface ocean imposes regional variation. Additional regional variation may be caused by sulfide formation and associated isotope fractionation in euxinic environments. The impact of such regional environmental conditions on the Cd- and Zn-isotope composition of the sediment therefore needs to be addressed in order to explore the use of these elements as a proxy for past nutrient conditions. Here we present an extensive dataset of cadmium- and zinc-isotope compositions of organic-rich marine sediments from different basins deposited during OAE 2 (Late Cretaceous). This comparison highlights regional differences in Cd- and Zn-isotope compositions. However, despite regional environmental controls, a correlation between δ114Cd and δ66Zn across the different sites is observed, which implies a largely similar control on the two isotope systems. When regional environmental controls are accounted for, the data may provide insight in the δ66Zn and δ114Cd evolution of global seawater during OAE 2 as well as information on the global cycling of redox-sensitive micronutrients during the event

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

Kinetic control on Zn isotope signatures recorded in marine diatoms

NASA Astrophysics Data System (ADS)

Köbberich, Michael; Vance, Derek

2017-08-01

Marine diatoms dominate the oceanic cycle of the essential micronutrient zinc (Zn). The stable isotopes of zinc and other metals are increasingly used to understand trace metal micronutrient cycling in the oceans. One clear feature of the early isotope data is the heavy Zn isotope signature of the average oceanic dissolved pool relative to the inputs, potentially driven by uptake of light isotopes into phytoplankton cells and export to sediments. However, despite the fact that diatoms strip Zn from surface waters across the Antarctic polar front in the Southern Ocean, the local upper ocean is not isotopically heavy. Here we use culturing experiments to quantify the extent of Zn isotope fractionation by diatoms and to elucidate the mechanisms driving it. We have cultured two different open-ocean diatom species (T. oceanica and Chaetoceros sp.) in a series of experiments at constant medium Zn concentration but at bioavailable medium Fe ranging from limiting to replete. We find that T. oceanica can maintain high growth rates and Zn uptake rates over the full range of bioavailable iron (Fe) investigated, and that the Zn taken up has a δ66Zn that is unfractionated relative to that of the bioavailable free Zn in the medium. The studied representative of the genus Chaetoceros, on the other hand, shows more significantly reduced Zn uptake rates at low Fe and records more variable biomass δ66Zn signatures, of up to 0.85‰ heavier than the medium. We interpret the preferential uptake of heavy isotopes at extremely low Zn uptake rates as potentially due to either of the following two mechanisms. First, the release of extracellular polymeric substances (EPS), at low Fe levels, may preferentially scavenge heavy Zn isotopes. Second, the Zn uptake rate may be slow enough to establish pseudo-equilibrium conditions at the transporter site, with heavy Zn isotopes forming more stable surface complexes. Thus we find that, in our experiments, Fe-limitation exerts a key control that not only limits diatom growth, but also affects the Zn uptake physiology of diatoms. Uptake of heavy isotopes occurs under Fe-limiting conditions that drive extremely low Zn uptake rates. On the other hand, more rapid Zn uptake rates result in biomass that is indistinguishable from the external bioavailable free Zn pool. These experimental results can, in principle, explain the range of Zn isotopic compositions found in the real surface ocean, given the geographically variable interplay between Fe-limitation, Zn uptake rates, and the degree of organic complexation of oceanic Zn.

Isotopic Evidence of Unaccounted for Fe and Cu Erythropoietic Pathways

NASA Astrophysics Data System (ADS)

Albarede, F.; Telouk, P.; Lamboux, A.; Jaouen, K.; Balter, V.

2011-12-01

Despite its potential importance for understanding perturbations in the Fe-Cu homeostatic pathways, the natural isotopic variability of these metals in the human body remains unexplored. We measured the Fe, Cu, and Zn isotope compositions of total blood, serum, and red blood cells of ~50 young blood donors by multiple-collector ICP-MS after separation and purification by anion exchange chromatography. Zn is on average 0.2 permil heavier in erythrocytes (δ 66Zn=0.44±0.33 permil) with respect to serum but shows much less overall isotopic variability than Fe and Cu, which indicates that isotope fractionation depends more on redox conditions than on ligand coordination. On average, Fe in erythrocytes (δ 56Fe=-2.59±0.47 permil) is isotopically light by 1-2 permil with respect to serum, whereas Cu in erythrocytes (δ 65Cu=0.56±0.50 permil) is 0.8 percent heavier. Fe and Cu isotope compositions clearly separate erythrocytes of men and women. Fe and Cu from B-type men erythrocytes are visibly more fractionated than all the other blood types. Isotope compositions provide an original method for evaluating metal mass balance and homeostasis. Natural isotope variability shows that the current models of Fe and Cu erythropoiesis, which assume that erythropoiesis is restricted to bone marrow, violate mass balance requirements. It unveils unsuspected major pathways for Fe, with erythropoietic production of isotopically heavy ferritin and hemosiderin, and for Cu, with isotopically light Cu being largely channeled into blood and lymphatic circulation rather than into superoxide dismutase-laden erythrocytes. Iron isotopes provide an intrinsic measuring rod of the erythropoietic yield, while Cu isotopes seem to gauge the relative activity of erythropoiesis and lymphatics.

Transpiration flow controls Zn transport in Brassica napus and Lolium multiflorum under toxic levels as evidenced from isotopic fractionation

NASA Astrophysics Data System (ADS)

Couder, Eléonore; Mattielli, Nadine; Drouet, Thomas; Smolders, Erik; Delvaux, Bruno; Iserentant, Anne; Meeus, Coralie; Maerschalk, Claude; Opfergelt, Sophie; Houben, David

2015-11-01

Stable zinc (Zn) isotope fractionation between soil and plant has been used to suggest the mechanisms affecting Zn uptake under toxic conditions. Here, changes in Zn isotope composition in soil, soil solution, root and shoot were studied for ryegrass (Lolium multiflorum L.) and rape (Brassica napus L.) grown on three distinct metal-contaminated soils collected near Zn smelters (total Zn 0.7-7.5%, pH 4.8-7.3). The Zn concentrations in plants reflected a toxic Zn supply. The Zn isotopic fingerprint of total soil Zn varied from -0.05‰ to +0.26 ± 0.02‰ (δ66Zn values relative to the JMC 3-0749L standard) among soils, but the soil solution Zn was depleted in 66Zn, with a constant Zn isotope fractionation of about -0.1‰ δ66Zn unit compared to the bulk soil. Roots were enriched with 66Zn relative to soil solution (δ66Znroot - δ66Znsoil solution = Δ66Znroot-soil solution = +0.05 to +0.2 ‰) and shoots were strongly depleted in 66Zn relative to roots (Δ66Znshoot-root = -0.40 to -0.04 ‰). The overall δ66Zn values in shoots reflected that of the bulk soil, but were lowered by 0.1-0.3 ‰ units as compared to the latter. The isotope fractionation between root and shoot exhibited a markedly strong negative correlation (R2 = 0.83) with transpiration per unit of plant weight. Thus, the enrichment with light Zn isotopes in shoot progressed with increasing water flux per unit plant biomass dry weight, showing a passive mode of Zn transport by transpiration. Besides, the light isotope enrichment in shoots compared to roots was larger for rape than for rye grass, which may be related to the higher Zn retention in rape roots. This in turn may be related to the higher cation exchange capacity of rape roots. Our finding can be of use to trace the biogeochemical cycles of Zn and evidence the tolerance strategies developed by plants in Zn-excess conditions.

Investigating the effects of abyssal peridotite alteration on Si, Mg and Zn isotopes

NASA Astrophysics Data System (ADS)

Savage, P. S.; Wimpenny, J.; Harvey, J.; Yin, Q.; Moynier, F.

2013-12-01

Around 1/3 of Earth's divergent ridge system is now classified as "slow" spreading [1], exposing ultramafic rocks (abyssal peridotites) at the seafloor. Such material is often highly altered by serpentinisation and steatisation (talc formation). It is crucial to understand such processes in order to access the original composition of the mantle, and to quantify any impact on ocean composition. Here we examine the effect of both serpentinisation and steatisation on Si, Mg and Zn isotopes. Hydrothermal alteration and seafloor weathering are both sources of oceanic Si [2] and weathering of abyssal peridotites is a source of oceanic Mg [3]; hence isotopic fractionation as a result of seafloor alteration could affect oceanic Si and Mg isotope composition. Zinc isotopes can provide complimentary information; the magnitude and direction of fractionation is highly dependent on complexing ligand [4] and can provide compositional information on the fluids driving metasomatism. For this study, two cores from the well-characterised abyssal peridotites recovered on ODP Leg 209 were examined [5]. Hole 1274a peridotites exhibit variable serpentinisation at ~200°C, whereas samples from Hole 1268a have been comprehensively serpentinised and then subsequently steatised to talc facies at ~350°C, by a low Mg/Si, low pH fluid. The Si, Mg and Zn isotope compositions of 1274a samples are extremely homogeneous, identical to that of pristine mantle rocks (BSE) i.e., serpentinisation at this locality was predominantly isochemical [5]. In contrast, samples from 1268a show greater isotopic variability. In all samples, Mg is enriched in the heavier isotopes relative to BSE, consistent with formation of isotopically heavy secondary phases [6]. For Si, serpentinised samples are slightly enriched in the lighter isotopes compared to BSE, again consistent with the behaviour of Si during formation of secondary phases [7]. Within the steatised samples, some exhibit enrichments in the lighter Si isotopes (similar to the serpentinites), however, some are isotopically heavy, relative to BSE. Such samples were found to have abundant chlorite, whose formation requires fluid with high Al activity, likely sourced from late-emplaced gabbroic dykes. The Zn of all 1268a samples are enriched in the lighter isotopes, implying the involvement of isotopically light sulfide precipitation during metasomatism [4]. The consistently heavy Mg isotope data suggest that seafloor alteration of peridotites can input an isotopically light Mg-bearing fluid to the ocean. Fluid composition is less easy to determine from the more complex behaviour observed in Si isotopes, although it is unlikely to substantially deviate from BSE, consistent with previous observations [8]. Finally, the strong enrichment in the lighter isotopes of Zn confirms that this isotope system could be used as a tracer of recycled serpentinised material at arc settings, as suggested in [4]. [1] Dick et al. (2003) Nature 426, 405-412; [2] Treguer and De La Rocha (2013) Ann. Rev. Mar. Sci. 5, 477-501; [3] Snow & Dick (1995) GCA, 59, 4219-4235; [4] Pons et al. (2011) PNAS 108(43) 17639-17643; [5] Bach et al., (2004) G3 5; [6] Tipper et al. (2006) EPSL 247, 267-279; [7] Opfergelt et al. (2012) Chem. Geol. 326, 113-122; [8] De La Rocha et al. (2000) GCA 64, 2467-2477.

Zinc isotopic composition of particulate matter generated during the combustion of coal and coal + tire-derived fuels

USGS Publications Warehouse

Borrok, D.M.; Gieré, R.; Ren, M.; Landa, E.R.

2010-01-01

Atmospheric Zn emissions from the burning of coal and tire-derived fuel (TDF) for power generation can be considerable. In an effort to lay the foundation for tracking these contributions, we evaluated the Zn isotopes of coal, a mixture of 95 wt % coal + 5 wt % TDF, and the particulate matter (PM) derived from their combustion in a power-generating plant. The average Zn concentrations and δ(66)Zn were 36 mg/kg and 183 mg/kg and +0.24‰ and +0.13‰ for the coal and coal + TDF, respectively. The δ(66)Zn of the PM sequestered in the cyclone-type mechanical separator was the lightest measured, -0.48‰ for coal and -0.81‰ for coal+TDF. The δ(66)Zn of the PM from the electrostatic precipitator showed a slight enrichment in the heavier Zn isotopes relative to the starting material. PM collected from the stack had the heaviest δ(66)Zn in the system, +0.63‰ and +0.50‰ for the coal and coal + TDF, respectively. Initial fractionation during the generation of a Zn-rich vapor is followed by temperature-dependent fractionation as Zn condenses onto the PM. The isotopic changes of the two fuel types are similar, suggesting that their inherent chemical differences have only a secondary impact on the isotopic fractionation process.

Zinc isotopic composition of particulate matter generated during the combustion of coal and coal + tire-derived fuels.

PubMed

Borrok, David M; Gieré, Reto; Ren, Minghua; Landa, Edward R

2010-12-01

Atmospheric Zn emissions from the burning of coal and tire-derived fuel (TDF) for power generation can be considerable. In an effort to lay the foundation for tracking these contributions, we evaluated the Zn isotopes of coal, a mixture of 95 wt % coal + 5 wt % TDF, and the particulate matter (PM) derived from their combustion in a power-generating plant. The average Zn concentrations and δ(66)Zn were 36 mg/kg and 183 mg/kg and +0.24‰ and +0.13‰ for the coal and coal + TDF, respectively. The δ(66)Zn of the PM sequestered in the cyclone-type mechanical separator was the lightest measured, -0.48‰ for coal and -0.81‰ for coal+TDF. The δ(66)Zn of the PM from the electrostatic precipitator showed a slight enrichment in the heavier Zn isotopes relative to the starting material. PM collected from the stack had the heaviest δ(66)Zn in the system, +0.63‰ and +0.50‰ for the coal and coal + TDF, respectively. Initial fractionation during the generation of a Zn-rich vapor is followed by temperature-dependent fractionation as Zn condenses onto the PM. The isotopic changes of the two fuel types are similar, suggesting that their inherent chemical differences have only a secondary impact on the isotopic fractionation process.

Zn and C isotopic evidence of climatic change during the Marinoan

NASA Astrophysics Data System (ADS)

Thiemens, M. M.; Moynier, F.; Koeberl, C.; Thiemens, M. H.; Shaheen, R.; Gyollai, I.; Popp, F.; Chong, K.

2011-12-01

The "Snowball Earth" events of the Cryogenian period are renowned for their remarkable chemical and isotopic signatures left in the geological record. Through analysis of post Marinoan glaciation cap carbonates from Namibia, specifically from Fransfontein, the Khowarib Valley, and Naraachamspos, a multi isotopic study was undertaken. We analyzed the δ 13C of chemically isolated calcite and dolomite. A moderate depletion of 13C in calcite (δ 13C<0% V-PDB) associated with global glaciations was observed, confirming the event. Associated dolomites also show a 13C depletion, but at a much lower magnitude. Zinc is a trace element that is necessary for all forms of life. Zn does not undergo redox cycling under normal environmental conditions, and biological uptake is one of the few processes that produces isotopic fractionation. This fractionation is in the range of 0.1 permil for the 66Zn/64Zn ratio (δ 66Zn in permil deviation), however with the advent of multi-collection inductively-coupled plasma mass spectrometry (MC-ICP-MS) such variations have become resolvable. We also have measured the Zinc composition of multiple species of lab cultured archaea, and found that the cells are enriched in the light isotopes of Zn compared to the culture medium. By measuring Zn levels in the Cap Carbonates, we seek corroboration for the carbon depletion we find during the glaciation. Zinc should undergo a similarly significant alteration at the mass extinction from climatic shifts inherent to a worldwide glaciation. We find the samples to be relatively consistent, with a δ 66Zn of approximately 0.30 to 0.40 in most places, with a δ 68Zn of double that, values typical of terrestrial rocks. Several sites have a much larger fractionation, with δ 66Zn of up to 0.90 in the Khowarib Valley, and up to 1.06 in the clays at the entrance to the South Valley. These isotopic compositions may be indicative of the massive climatic event leading to the formation of the cap carbonates.

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.

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.

Zinc Isotopes as Tracers of Crust-Mantle Interactions and Mineralization Processes in Layered Intrusions

NASA Astrophysics Data System (ADS)

Day, J. M.; Moynier, F.

2016-12-01

Zinc isotopes are a powerful tool for studying igneous processes and may be useful for distinguishing between mantle or crustal origins for mineralization and for examining crystallization processes. Restricted ranges in δ66Zn for mantle-derived rocks (δ66Zn = 0.28±0.05‰; [{66Zn/64Znsample/66Zn/64ZnJMC-Lyon-1} × 1000] all uncertainties reported are 2SD) contrast the large δ66Zn variations in sedimentary rocks ( 0 to 1‰), or in volcanic and sedimentary hosted ore deposits (e.g., SEDEX; VHMS; MVT = -0.6 to 1.3‰). Here, we use Zn isotopes to investigate magmatic processes in the 1.27 Ga Muskox Intrusion (Canada) and 2.7 Ga Stillwater Intrusion (Montana). The Muskox main chromitite horizon has between 270-330 ppm Zn with δ66Zn ranging from 0.16 to 0.31‰. Zinc isotope compositions negatively correlate with Os isotopes. Chromitite (40a) with the lowest 187Os/188Os (0.132) has δ66Zn of 0.31±0.03‰; indistinguishable from the mantle value. CM19 glass from the co-eval Coppermine Volcanics, which has crust-like O and Nd isotopes but low 187Os/188Os (0.131), has been interpreted as the extrusive manifestation of chromitite genesis. The value of δ66Zn (0.27±0.07‰) for CM19 is within uncertainty of 40A, and permissive of formation during silicic-mafic melt mixing and large-scale chromitite crystallization. Stillwater chromitite seams exhibit a larger range in Zn (166-448 ppm), but generally lower δ66Zn (0.13±0.04‰) than Muskox chromitites, or to a JM Reef bulk sample (69 ppm Zn, δ66Zn = 0.22±0.03‰). These results suggest different sources of Zn for Ultramafic series chromitites versus the JM Reef (Banded series). Correspondingly, variations occur in Os isotopes for PGE poor chromitites (γOs = -2 to +4) versus the PGE-rich JM Reef (γOs = +12 to +34). Zinc isotope variations may be explained by either a mantle source with low δ66Zn that was subsequently contaminated by high δ66Zn crust, or from contamination of the ultramafic series by low δ66Zn continental lithospheric mantle. JM Reef sulphides span a wide range in Zn (1.8-350 ppm) and δ66Zn (-0.03 to 0.68‰) consistent with fractionation of Zn isotopes during sulphide melt-mineral crystallization. These results show promise for using Zn isotopes to study sources of mineralization and to elucidate sulphide crystallization processes.

Isotopically distinct reservoirs in the solar nebula: Isotope anomalies in Vigarano meteorite inclusions

NASA Technical Reports Server (NTRS)

Loss, R. D.; Lugmair, G. W.; Davis, A. M.; Macpherson, G. J.

1994-01-01

The isotopic compositions of Mg, Ca, Ti, Cr, Zn, Sr, Ba, Nd, and Sm were measured in four relatively unaltered refractory inclusions from the Vigarano carbonaceous chondrite meteorite. Three of the inclusions (USNM 1623-2, 1623-3, and 1623-8) show similar Mg, Ca, Ti, and Cr isotopic compositions to those found in most inclusions in the Allende carbonaceous chondrite. This indicates that these Vigarano inclusions sampled the same isotopic reservoirs as the majority of the Allende inclusions that isotope signatures in the latter were not significantly modified by the secondary alteration that permeates most Allende inclusions. In contrast, inclusion 1623-5 has large deficits in Mg-26, Ca-48, and Ti-50 and small but distinct Cr-54, Zn-66, Sr-84, Ba-135, Ba-137, and Sm-144 anomalies. The magnitudes of these unusual anomalies in the refractory elements are within analytical uncertainty of those found in the Allende 'FUN" inclusion C1, yet 1623-5 has a very different bulk chemical composition from C1. The fact that 1623-5 and C1 have identical isotopic anomalies yet have significantly distinct major and trace element contents provide convincing evidence for the presence of isotopically distinct reservoirs in the early solar system.

Zinc and volatile element loss during planetary magma ocean phases

NASA Astrophysics Data System (ADS)

Dhaliwal, Jasmeet K.; Day, James M. D.; Moynier, Frédéric

2016-10-01

Zinc is a moderately volatile element and a key tracer of volatile depletion on planetary bodies due to lack of significant isotopic fractionation under high-temperature processes. Terrestrial basalts have δ66Zn values similar to some chondrites (+ 0.15 to 0.3‰ where [{66Zn/64Znsample/66Zn/64ZnJMC-Lyon-1} × 1000]) and elevated Zn concentrations (100 ppm). Lunar mare basalts yield a mean δ66Zn value of +1.4 ± 0.5‰ and have low Zn concentrations (~2 ppm). Late-stage lunar magmatic products, such as ferroan anorthosite, Mg-suite and Alkali suite rocks exhibit heavier δ66Zn values (+3 to +6‰). The heavy δ66Zn lunar signature is thought to reflect evaporative loss and fractionation of zinc, either during a giant impact or in a magma ocean phase.We explore conditions of volatile element loss within a lunar magma ocean (LMO) using models of Zn isotopic fractionation that are widely applicable to planetary magma oceans. For the Moon, our objective was to identify conditions that would yield a δ66Zn signature of ~ +1.4‰ within the mantle, assuming a terrestrial mantle zinc starting composition.We examine two cases of zinc evaporative fractionation: (1) lunar surface zinc fractionation that was completed prior to LMO crystallization and (2) lunar surface zinc fractionation that was concurrent with LMO crystallization. The first case resulted in a homogeneous lunar mantle and the second case yielded a stratified lunar mantle, with the greatest zinc isotopic enrichment in late-stage crystallization products. This latter case reproduces the distribution of zinc isotope compositions in lunar materials quite well.We find that hydrodynamic escape was not a dominant process in losing Zn, but that erosion of a nascent lunar atmosphere, or separation of condensates into a proto-lunar crust are possible. While lunar volatile depletion is still possible as a consequence of the giant impact, this process cannot reproduce the variable δ66Zn found in the Moon. Outgassing during magma ocean phases would have led to volatile-depleted planetesimal feed-stocks that would have profoundly affected the ultimate volatile inventories of larger planetary bodies.

Interaction between zinc and freshwater and marine diatom species: Surface complexation and Zn isotope fractionation

NASA Astrophysics Data System (ADS)

Gélabert, A.; Pokrovsky, O. S.; Viers, J.; Schott, J.; Boudou, A.; Feurtet-Mazel, A.

2006-02-01

This work is devoted to characterization of zinc interaction in aqueous solution with two marine planktonic ( Thalassiosira weissflogii = TW, Skeletonema costatum = SC) and two freshwater periphytic species ( Achnanthidium minutissimum = AMIN, Navicula minima = NMIN) by combining adsorption and electrophoretic measurements with surface complexation modeling and by assessing Zn isotopes fractionation during both long term uptake and short term adsorption on diatom cells and their frustules. Reversible adsorption experiments were performed at 25 and 5 °C as a function of exposure time (5 min to 140 h), pH (2 to 10), zinc concentration in solution (10 nM to 1 mM), ionic strength ( I = 0.001 to 1.0 M) and the presence of light. While the shape of pH-dependent adsorption edge is almost the same for all four species, the constant-pH adsorption isotherm and maximal Zn binding capacities differ by an order of magnitude. The extent of adsorption increases with temperature from 5 to 25 °C and does not depend on light intensity. Zinc adsorption decreases with increase of ionic strength suggesting competition with sodium for surface sites. Cell number-normalized concentrations of sorbed zinc on whole cells and their silica frustules demonstrated only weak contribution of the latter (10-20%) to overall zinc binding by diatom cell wall. Measurements of electrophoretic mobilities ( μ) revealed negative diatoms surface potential in the full range of zinc concentrations investigated (0.15-760 μmol/L), however, the absolute value of μ decreases at [Zn] > 15 μmol/L suggesting a change in surface speciation. These observations allowed us to construct a surface complexation model for Zn binding by diatom surfaces that postulates the constant capacitance of the electric double layer and considers Zn complexation with carboxylate and silanol groups. Thermodynamic and structural parameters of this model are based on previous acid-base titration and spectroscopic results and allow quantitative reproduction of all adsorption experiments. Although Zn adsorption constants on carboxylate groups are almost the same, Zn surface adsorption capacities are very different among diatom species which is related to the systematic differences in their cell wall composition and thickness. Measurements of Zn isotopic composition ( 66Zn/( 64Zn)) performed using a multicollector ICP MS demonstrated that irreversible incorporation of Zn in cultured diatom cells produces enrichment in heavy isotope compared to growth media (Δ 66Zn(solid-solution) = 0.27 ± 0.05, 0.08 ± 0.05, 0.21 ± 0.05, and 0.19 ± 0.05‰ for TW, SC, NMIN, and AMIN species, respectively). Accordingly, an enrichment of cells in heavy isotopes (Δ 66Zn(solid-solution) = 0.43 ± 0.1 and 0.27 ± 0.1‰ for NMIN and AMIN, respectively) is observed following short-term Zn sorption on freshwater cells in nutrient media at pH ˜ 7.8. Finally, diatoms frustules are enriched in heavy isotopes compared to solution during Zn adsorption on silica shells at pH ˜ 5.5 (Δ 66Zn(solid-solution) = 0.35 ± 0.10‰). Measured isotopes fractionation can be related to the structure and stability of Zn complexes formed and they provide a firm basis for using Zn isotopes for biogeochemical tracing.

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.

Determining provenance of marine metal pollution in French bivalves using Cd, Zn and Pb isotopes

NASA Astrophysics Data System (ADS)

Shiel, Alyssa E.; Weis, Dominique; Cossa, Daniel; Orians, Kristin J.

2013-11-01

Cadmium, Zn and Pb isotopic compositions (MC-ICP-MS) and elemental concentrations (HR-ICP-MS) have been used to distinguish between natural and anthropogenic sources of these metals in bivalves collected from the coastlines of France (English Channel, Atlantic and Mediterranean coasts). The Cd isotopic signatures (δ114Cd = -1.08‰ to -0.52‰) exhibited by bivalves from the coastlines of France, excluding those from NE France, are within the range of those exhibited by bivalves from the USA East coast (δ114Cd = -1.20‰ to -0.54‰). This indicates the high prevalence of industry, as well as the low natural contributions of Cd from North Atlantic waters in both regions. Thus, the significance of anthropogenic Cd sources is similar. These significant anthropogenic contributions are identified for bivalves with a large range in tissue Cd concentrations. Importantly, French bivalves from the Gironde estuary and Marennes-Oléron basin (regions of historic and modern importance for oyster farming, respectively) exhibited the highest Cd levels of the study. Their Cd isotopic signatures indicate historical smelting emissions remain the primary Cd source despite the cessation of local smelting activities in 1986 and subsequent remedial efforts. No significant variability is observed in the δ66Zn values of the French bivalves (∼0.53‰), with the exception of the much heavier compositions exhibited by oysters from the polluted Gironde estuary (1.19-1.27‰). Lead isotopes do not fractionate during processing like Cd and Zn. They can, therefore, be used to identify emissions from industrial processes and the consumption of unleaded gasoline and diesel fuel as metal sources to French bivalves. Cadmium and Zn isotopes are successfully used here as tracers of anthropogenic processing emissions and are combined with Pb isotope "fingerprinting" techniques to identify metal sources.

Volatile element loss during planetary magma ocean phases

NASA Astrophysics Data System (ADS)

Dhaliwal, Jasmeet K.; Day, James M. D.; Moynier, Frédéric

2018-01-01

Moderately volatile elements (MVE) are key tracers of volatile depletion in planetary bodies. Zinc is an especially useful MVE because of its generally elevated abundances in planetary basalts, relative to other MVE, and limited evidence for mass-dependent isotopic fractionation under high-temperature igneous processes. Compared with terrestrial basalts, which have δ66Zn values (per mille deviation of the 66Zn/64Zn ratio from the JMC-Lyon standard) similar to some chondrite meteorites (∼+0.3‰), lunar mare basalts yield a mean δ66Zn value of +1.4 ± 0.5‰ (2 st. dev.). Furthermore, mare basalts have average Zn concentrations ∼50 times lower than in typical terrestrial basaltic rocks. Late-stage lunar magmatic products, including ferroan anorthosite, Mg- and Alkali-suite rocks have even higher δ66Zn values (+3 to +6‰). Differences in Zn abundance and isotopic compositions between lunar and terrestrial rocks have previously been interpreted to reflect evaporative loss of Zn, either during the Earth-Moon forming Giant Impact, or in a lunar magma ocean (LMO) phase. To explore the mechanisms and processes under which volatile element loss may have occurred during a LMO phase, we developed models of Zn isotopic fractionation that are generally applicable to planetary magma oceans. Our objective was to identify conditions that would yield a δ66Zn signature of ∼+1.4‰ within the lunar mantle. For the sake of simplicity, we neglect possible Zn isotopic fractionation during the Giant Impact, and assumed a starting composition equal to the composition of the present-day terrestrial mantle, assuming both the Earth and Moon had zinc 'consanguinity' following their formation. We developed two models: the first simulates evaporative fractionation of Zn only prior to LMO mixing and crystallization; the second simulates continued evaporative fractionation of Zn that persists until ∼75% LMO crystallization. The first model yields a relatively homogenous bulk solid LMO δ66Zn value, while the second results in a stratification of δ66Zn values within the LMO sequence. Loss and/or isolation mechanisms for volatiles are critical to these models; hydrodynamic escape was not a dominant process, but loss of a nascent lunar atmosphere or separation of condensates into a proto-lunar crust are possible mechanisms by which volatiles could be separated from the lunar interior. The results do not preclude models that suggest a lunar volatile depletion episode related to the Giant Impact. Conversely, LMO models for volatile loss do not require loss of volatiles prior to lunar formation. Outgassing during planetary magma ocean phases likely played a profound role in setting the volatile inventories of planets, particularly for low mass bodies that experienced the greatest volatile loss. In turn, our results suggest that the initial compositions of planets that accreted from smaller, highly differentiated planetesimals were likely to be severely volatile depleted.

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.

Gallium isotopic evidence for the fate of moderately volatile elements in planetary bodies and refractory inclusions

NASA Astrophysics Data System (ADS)

Kato, Chizu; Moynier, Frédéric

2017-12-01

The abundance of moderately volatile elements, such as Zn and Ga, show variable depletion relative to CI between the Earth and primitive meteorite (chondrites) parent bodies. Furthermore, the first solar system solids, the calcium-aluminum-rich inclusions (CAIs), are surprisingly rich in volatile element considering that they formed under high temperatures. Here, we report the Ga elemental and isotopic composition of a wide variety of chondrites along with five individual CAIs to understand the origin of the volatile elements and to further characterize the enrichment of the volatile elements in high temperature condensates. The δ71Ga (permil deviation of the 71Ga/69Ga ratio from the Ga IPGP standard) of carbonaceous chondrites decreases in the order of CI >CM >CO >CV and is inversely correlated with the Al/Ga ratio. This implies that the Ga budget of the carbonaceous chondrites parent bodies were inherited from a two component mixing of a volatile rich reservoir enriched in heavy isotope of Ga and a volatile poor reservoir enriched in light isotope of Ga. Calcium-aluminum-rich inclusions are enriched in Ga and Zn compared to the bulk meteorite and are both highly isotopically fractionated with δ71Ga down to -3.56‰ and δ66Zn down to -0.74‰. The large enrichment in the light isotopes of Ga and Zn in the CAIs implies that the moderately volatile elements were introduced in the CAIs during condensation in the solar nebula as opposed to secondary processing in the meteorite parent body and supports a change in gas composition in which CAIs were formed.

Biogeochemical cycling of zinc and its isotopes in the Southern Ocean

NASA Astrophysics Data System (ADS)

Zhao, Y.; Vance, D.; Abouchami, W.; de Baar, H. J. W.

2014-01-01

We report Zn concentration and isotope data for seawater samples from the Atlantic sector of the Southern Ocean, collected during the IPY/GEOTRACES ANT-XXIV/III cruise along the Greenwich Zero Meridian. Data are reported for the full depth range of the water column at three stations, as well as a transect of surface samples, using a new analytical approach that is presented in detail here. Zn concentrations increase with depth, though due to proximity to upwelling sites, surface concentrations are not as low as in some parts of the ocean such as further northward into the Sub-Antarctic Zone. For two depth profiles south of the Polar Front Zone, the physical stratification of the upper water column is reflected in sudden near-surface changes in Zn concentration with depth. In contrast, beneath 100-300 m Zn concentrations barely change with depth. Zn isotopic data beneath 1000 m, for the Southern Ocean data presented here as well as published data from the North Atlantic and North Pacific, are strikingly homogeneous, with an average δ66Zn = +0.53 ± 0.14‰ (2SD, 2SE = 0.03, n = 21). The surface Southern Ocean is more variable, with δ66Zn ranging from 0.07‰ to 0.80‰. Between the two is a thin horizon at 40-80 m which, in the Southern Ocean as well as the North Atlantic and North Pacific, is characterised by distinctly light isotopic signatures, with δ66Zn about 0.3‰ lower than surface waters. Strong correlations between Si and Zn concentrations seen here and elsewhere, coupled to the lack of any systematic relationship between Si and Zn isotopes in the Southern Ocean, suggest that the removal of Zn associated with diatom opal involves little or no isotopic fractionation. Regeneration of this Zn also explains the homogeneous Zn isotopic composition of the global deep ocean so far sampled. However, the low Zn content of opal requires that deep ocean Zn does not directly come from the opal phase itself, but rather from associated organic material external to the diatom frustule during growth. Experimental data are consistent with little or no fractionation during incorporation of Zn into this material. On the other hand, the light zinc at 40-80 m is most consistent with the regeneration of an intra-cellular pool that both culturing experiments and field data suggest will be isotopically light. The data thus imply two processes by which Zn is taken up in the surface ocean, that these pools have very different regeneration lengthscales, and that physical mixing of the oceans cannot eradicate their isotopic signatures. Finally, the deep δ66Zn ocean value is significantly higher than the current best estimate of the input to the oceans. The most obvious candidate for the required light sink is the survival of some of the cellular Zn to be buried in sediment.

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.

The estuarine geochemical reactivity of Zn isotopes and its relevance for the biomonitoring of anthropogenic Zn and Cd contaminations from metallurgical activities: Example of the Gironde fluvial-estuarine system, France

NASA Astrophysics Data System (ADS)

Petit, Jérôme C. J.; Schäfer, Jörg; Coynel, Alexandra; Blanc, Gérard; Chiffoleau, Jean-François; Auger, Dominique; Bossy, Cécile; Derriennic, Hervé; Mikolaczyk, Mathilde; Dutruch, Lionel; Mattielli, Nadine

2015-12-01

Zinc stable isotopes measurements by MC-ICP-MS, validated by laboratory intercalibrations, were performed on wild oysters, suspended particles and filtered river/estuarine water samples to provide new constraints for the use of Zn isotopes as environmental tracers. The samples selected were representative of the long range (400 km) transport of metal (Zn, Cd, etc.) contamination from former Zn-refining activities at Decazeville (i.e. δ66Zn > 1‰) and its phasing out, recorded during 30 years in wild oysters from the Gironde Estuary mouth (RNO/ROCCH sample bank). The study also addresses additional anthropogenic sources (urban and viticulture) and focuses on geochemical reactivity of Zn in the turbidity gradient and the maximum turbidity zone (MTZ) of the fluvial Gironde Estuary. In this area, dissolved Zn showed a strong removal onto suspended particulate matter (SPM) and progressive enrichment in heavy isotopes with increasing SPM concentrations varying from δ66Zn = -0.02‰ at 2 mg/L to +0.90‰ at 1310 mg/L. These signatures were attributed to kinetically driven adsorption due to strongly increasing sorption sites in the turbidity gradient and MTZ of the estuary. Oysters from the estuary mouth, contaminated sediments from the Lot River and SPM entering the estuary showed parallel historical evolutions (1979-2010) for Zn/Cd ratios but not for δ66Zn values. Oysters had signatures varying from δ66Zn = 1.43‰ in 1983 to 1.18‰ in 2010 and were offset by δ66Zn = 0.6-0.7‰ compared to past (1988) and present SPM from the salinity gradient. Isotopic signatures in river-borne particles entering the Gironde Estuary under contrasting freshwater discharge regimes during 2003-2011 showed similar values (δ66Zn ≈ 0.35 ± 0.03‰; 1SD, n = 15), i.e. they were neither related to former metal refining activities at least for the past decade nor clearly affected by other anthropogenic sources. Therefore, the Zn isotopic signatures in Gironde oysters reflect the geochemical reactivity of Zn in the estuary rather than signatures of past metallurgical contaminations in the watershed as recorded in contaminated river sediments. The study also shows that the isotopic composition of Zn is strongly fractionated by its geochemical reactivity in the Gironde Estuary, representative of meso-macrotidal estuarine systems.

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.

Rubidium Isotope Composition of the Earth and the Moon: Evidence for the Origin of Volatile Loss During Planetary Accretion

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Moynier, F.

2016-12-01

The Earth-Moon system has a variety of chemical and isotopic characteristics that provide clues to understanding the mechanism of lunar formation. One important observation is the depletion in moderately volatile elements in the Moon compared to the Earth. This volatile element depletion may be a signature of volatile loss during the Moon-forming Giant Impact. Stable isotopes are powerful tracers of such a process, since volatile loss via evaporation enriches the residue in heavy isotopes. However, early studies searching for the fingerprint of volatile loss failed to find any resolvable variations [1]. Recent work has now revealed heavy isotope enrichments in the Moon relative to the Earth for the moderately volatile elements Zn [2,3] and K [4]. The purely lithophile nature of Rb (in contrast to the chalcophile/lithophile nature of Zn) and the higher volatility of Rb compared to K make Rb an ideal element with which to study the origin of lunar volatile element depletion. We have developed a new method for the high-precision measurement of Rb isotope ratios by MC-ICP-MS. The Rb isotope compositions of terrestrial rocks define a narrow range, indicating that Rb isotope fractionation during igneous differentiation is limited (<30 ppm/amu). There is a clear signature of Rb loss during evaporation in volatile-depleted achondrites and lunar rocks. In particular, eucrites are significantly enriched in 87Rb (up to several per mil) relative to chondrites. Similarly, lunar basalts are enriched in 87Rb compared to terrestrial basalts, by 200 ppm for 87Rb/85Rb. These data are the first measurements of a resolvable difference in Rb isotope composition between the Earth and the Moon. The variations in Rb isotope composition between the Earth and the Moon are consistent with Rb isotope fractionation due to evaporation. References: [1] Humayun & Clayton GCA 1995. [2] Paniello et al. Nature 2012. [3] Kato et al. Nat. Comm. 2015. [4] Wang and Jacobsen Nature in press.

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.

Combining XAS speciation and Zn isotopes to track past eutrophication in lake sediments : The example of Baldeggersee (Switzerland)

NASA Astrophysics Data System (ADS)

Noël, V. S.; Voegelin, A.; Jouvin, D.; Louvat, P.; gelabert, A.; Mueller, B.; Benedetti, M. F.; Juillot, F.

2011-12-01

Among transition elements, Zn has attracted a great deal of interest because it is an essential nutrient at low concentrations, but it can also be toxic when present at high concentrations in ecosystems (Morel et al., 2003). In the present study, the isotopic signature and crystal-chemical of Zn were followed along a sediment core from a prealpine lake that experienced a marked eutrophication in order to explore the potential of this approach at tracking past environmental conditions of continental lake-catchment systems. Lake Baldeggersee (Luzern, Switzerland) is located at an elevation of 900 m in the Swiss Prealps. It experienced a period of strong eutrophication due to intensive farming in its catchment (Lotter et al., 1997). These led to the formation of varved sediments over one century prior to artificial lake aeration (Wehrli et al., 1997). This enabled us to correlate Zn speciation and isotopic signatures to the history of the water column. Results indicate that both Zn speciation and isotopes are distinct between sediments deposited during mesotrophic and eutrophic conditions in the water column: During the mesotrophic period, sedimentation was mainly detrital and Zn is mainly found associated with clay minerals in the sediments. During the eutrophic period, sedimentation was dominated by biological activity in the lake and Zn mainly occurs as ZnS in the sediments. Zn isotopes recorded these changes in the sedimentation regime, with δ66ZnJMC values around +0.2 % for the sediments of the mesotrophic period and δ66ZnJMC values around 0 % for the sediments of the eutrophic period. Comparison with the results from a study on the seasonal variation of the isotope signature of Zn in settling sediment of another prealpine lake (Peel et al., 2010) suggests that the enrichment in light Zn isotopes in the eutrophic sediments is in line with predominant Zn input with settling biomass (algae). Since lake eutrophication is mainly related to hydrological conditions and occupancy of the related catchment, these results emphasize the great potential of such a combination of molecular level speciation and Zn isotopes in lake sediments cores to track paleo-climatic or paleo-environmental conditions in lake catchments. Lotter A.F., Sturm M., Teranes J.L. and Wehrli B. (1997) Varve fromation since 1885 and high-resolution varve analyses in hypertrophic Baldeggersee (Switzerland) Aquatic Sciences 59, 304-325. Morel F. M. M. and Price N. M. (2003) The biogeochemical cycles of trace metals in the oceans. Science 300, 944-947. Peel K., Weiss D., Sigg L. (2010) Zinc isotope composition of settling particles as a proxy for biogeochemical processes in lakes: Insights from the eutrophic Lake Greifen, Switzerland. Limnol. Oceanogr., 54(5), 1699-1708. Wehrli, B.; Lotter, A.F.; Schaller, T.; Sturm, M. (1997) High-resolution varve studies in Baldeggersee (Switzerland): Project overview and limnological background data. Aquatic Sciences 59, 285-294).

Tracing cadmium, zinc and lead sources in bivalves from the coasts of western Canada and the USA using isotopes

NASA Astrophysics Data System (ADS)

Shiel, Alyssa E.; Weis, Dominique; Orians, Kristin J.

2012-01-01

Environmental monitoring and remediation require techniques to identify the source and fate of metals emissions. The measurement of heavy metal isotopic signatures, made possible by the advent of the MC-ICP-MS, is a powerful new geochemical tool, which may be used to trace the source of these metals in the environment. In a multi-tracer study, Cd, Zn and Pb isotopic compositions (MC-ICP-MS) and elemental concentrations (HR-ICP-MS) are used to distinguish between natural and anthropogenic sources of these metals in bivalves collected from western Canada (British Columbia), Hawaii, and the USA East Coast. Variability in the δ 114/110Cd values of bivalves (-1.20‰ to -0.09‰) is attributed to differences in the relative contributions of Cd from natural and anthropogenic sources between sites. Cadmium isotopic compositions (δ 114/110Cd = -0.69‰ to -0.09‰) identify high Cd levels in B.C. oysters as primarily natural (i.e., upwelling of Cd rich intermediate waters in the North Pacific), with some variability attributed to anthropogenic sources (e.g., mining and smelting). Variability in the δ 66/64Zn values exhibited by the B.C. bivalves is relatively small (0.28-0.36‰). Despite the low Pb levels found in B.C. oysters, Pb isotopes are used to identify emissions from industrial processes and the consumption of unleaded gasoline and diesel fuel as significant metal sources. Although the Cd concentrations of the USA East Coast bivalves are primarily lower than those of B.C. oysters, their relatively light Cd isotopic compositions (δ 114/110Cd = -1.20‰ to -0.54‰) indicate the significance of anthropogenic Cd sources and are attributed to the high prevalence of industry on this coast. The δ 114/110Cd values of USA East Coast bivalves include the lightest ever reported, with the exception of values reported for extraterrestrial materials. In addition, the Pb isotopic compositions of bivalves from the USA East Coast indicate Pb emissions from the combustion of coal are an important source of Pb, consistent with the high consumption of coal for power production on this coast. 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 "fingerprinting" techniques.

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.

Temperature dependence of the A, B, and C excitons in ZnO over 5-400 K: A modulated reflectivity study.

NASA Astrophysics Data System (ADS)

Tsoi, S.; Cardona, M.; Lauck, R.; Alawadhi, H.; Lu, X.; Grimsditch, M.; Ramdas, A. K.

2005-03-01

Optical properties of ZnO, a wide gap semiconductor with wurtzite structure, have generated renewed interest in the material in the context of opto-electronic phenomena and applications. The A, B, and C excitons of ZnO, arising from the combined effects of crystal field and spin-orbit splittings of the valence band, are investigated in the temperature range 5- 400 K, exploiting electro-, photo-, and wavelength-modulated reflectivity. The specimens studied have natural isotopic composition. The temperature dependence of the A, B, and C excitonic band gaps, fitted with a two harmonic oscillator modelootnotetextM. Cardona, Phys. Status. Solidi b 220, 5 (2000); R. Pä'ssler, J. Appl. Phys. 89, 6235 (2001) following Manj'on et al.ootnotetextF. J. Manj'on et al., Solid State Commun. 128, 35 (2003), yields the magnitudes of the zero-point renormalizations 262 meV (A), 227 meV (B), and 249 meV (C), respectively. Isotopically controlled ZnO is currently being investigated to determine the isotopic mass dependence of the zero-point renormalizations.

Effects of surface structural disorder and surface coverage on isotopic fractionation during Zn(II) adsorption onto quartz and amorphous silica surfaces

DOE PAGES

Nelson, Joey; Wasylenki, Laura; Bargar, John R.; ...

2017-08-05

Metal ion-mineral surface interactions and the attendant isotopic fractionation depend on the properties of the mineral surface and the local atomic-level chemical environment. Furthermore, these factors have not been systematically examined for phases of the same composition with different levels of surface disorder.

Effects of surface structural disorder and surface coverage on isotopic fractionation during Zn(II) adsorption onto quartz and amorphous silica surfaces

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

Nelson, Joey; Wasylenki, Laura; Bargar, John R.

Metal ion-mineral surface interactions and the attendant isotopic fractionation depend on the properties of the mineral surface and the local atomic-level chemical environment. Furthermore, these factors have not been systematically examined for phases of the same composition with different levels of surface disorder.

Assessing the dietary bioavailability of metals associated with natural particles: Extending the use of the reverse labeling approach to zinc

USGS Publications Warehouse

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

2017-01-01

We extend the use of a novel tracing technique to quantify the bioavailability of zinc (Zn) associated with natural particles using snails enriched with a less common Zn stable isotope. Lymnaea stagnalis is a model species that has relatively fast Zn uptake rates from the dissolved phase, enabling their rapid enrichment in 67Zn during the initial phase of labeling. Isotopically enriched snails were subsequently exposed to algae mixed with increasing amounts of metal-rich particles collected from two acid mine drainage impacted rivers. Zinc bioavailability from the natural particles was inferred from calculations of 66Zn assimilation into the snail’s soft tissues. Zinc assimilation efficiency (AE) varied from 28% for the Animas River particles to 45% for the Snake River particles, indicating that particle-bound, or sorbed Zn, was bioavailable from acid mine drainage wastes. The relative binding strength of Zn sorption to the natural particles was inversely related to Zn bioavailability; a finding that would not have been possible without using the reverse labeling approach. Differences in the chemical composition of the particles suggest that their geochemical properties may influence the extent of Zn bioavailability.

Assessing the Dietary Bioavailability of Metals Associated with Natural Particles: Extending the Use of the Reverse Labeling Approach to Zinc.

PubMed

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

2017-03-07

We extend the use of a novel tracing technique to quantify the bioavailability of zinc (Zn) associated with natural particles using snails enriched with a less common Zn stable isotope. Lymnaea stagnalis is a model species that has relatively fast Zn uptake rates from the dissolved phase, enabling their rapid enrichment in 67 Zn during the initial phase of labeling. Isotopically enriched snails were subsequently exposed to algae mixed with increasing amounts of metal-rich particles collected from two acid mine drainage impacted rivers. Zinc bioavailability from the natural particles was inferred from calculations of 66 Zn assimilation into the snail's soft tissues. Zinc assimilation efficiency (AE) varied from 28% for the Animas River particles to 45% for the Snake River particles, indicating that particle-bound, or sorbed Zn, was bioavailable from acid mine drainage wastes. The relative binding strength of Zn sorption to the natural particles was inversely related to Zn bioavailability; a finding that would not have been possible without using the reverse labeling approach. Differences in the chemical composition of the particles suggest that their geochemical properties may influence the extent of Zn bioavailability.

Mercury Isotopes as Proxies to Identify Sources and Environmental Impacts of Mercury in Sphalerites

PubMed Central

Yin, Runsheng; Feng, Xinbin; Hurley, James P.; Krabbenhoft, David P.; Lepak, Ryan F.; Hu, Ruizhong; Zhang, Qian; Li, Zhonggen; Bi, Xianwu

2016-01-01

During the past few years, evidence of mass independent fractionation (MIF) for mercury (Hg) isotopes have been reported in the Earth’s surface reservoirs, mainly assumed to be formed during photochemical processes. However, the magnitude of Hg-MIF in interior pools of the crust is largely unknown. Here, we reported significant variation in Hg-MIF signature (Δ199Hg: −0.24 ~ + 0.18‰) in sphalerites collected from 102 zinc (Zn) deposits in China, indicating that Hg-MIF can be recorded into the Earth’s crust during geological recycling of crustal material. Changing magnitudes of Hg-MIF signals were observed in Zn deposits with different formations, evidence that Hg isotopes (especially Hg-MIF) can be a useful tracer to identify sources (syngenetic and epigenetic) of Hg in mineral deposits. The average isotopic composition in studied sphalerites (δ202Hgaverage: −0.58‰; Δ199Hgaverage: +0.03‰) may be used to fingerprint Zn smelting activities, one of the largest global Hg emission sources. PMID:26728705

The fate of moderately volatile elements during planetary formation in the inner Solar System

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Moynier, F.

2017-12-01

Moderately volatile element abundances are variable among inner Solar System bodies, with differing degrees of depletion compared to chondrites. These variations are a consequence of the processes of planetary formation. The conditions and the specific mechanisms of planetary accretion and differentiation can be investigated by analyzing the stable isotope compositions of terrestrial and extraterrestrial samples. The moderately volatile lithophile elements are particularly useful to distinguish between the effects of accretion and those of core formation. Recent work has shown isotope variations in inner Solar System bodies for the moderately volatile elements Zn and K. The purely lithophile nature of Rb (in contrast to Zn) and the higher volatility of Rb compared to K make Rb an ideal element with which to further study moderately volatile element depletion. We have developed a new method for the high-precision measurement of Rb isotope ratios by MC-ICP-MS. Terrestrial rocks define a narrow range in Rb isotope composition, indicating that Rb isotope fractionation during igneous differentiation is limited (<30 ppm/amu). Larger Rb isotope variations are observed in extraterrestrial materials. Carbonaceous chondrites display a trend toward lighter Rb isotope composition coupled with decreasing Rb/Sr, opposite to the effect expected if their volatile element variations were caused by evaporative loss of Rb. This relationship indicates that the volatile element abundance variations in carbonaceous chondrites are not due to evaporation or condensation, but rather are due to the mixing of chemically and isotopically distinct primordial reservoirs. In contrast, there is a clear signature of Rb loss during evaporation in volatile-depleted achondrites and lunar rocks. Significant heavy isotope enrichments (up to several per mil for 87Rb/85Rb) are found for volatile-depleted planetesimals, including eucrites. In addition, lunar rocks also display heavy Rb isotope enrichments compared to the BSE. The most likely cause of these variations is Rb isotope fractionation due to evaporation during accretion.

Zinc isotope evidence for sulfate-rich fluid transfer across subduction zones.

PubMed

Pons, Marie-Laure; Debret, Baptiste; Bouilhol, Pierre; Delacour, Adélie; Williams, Helen

2016-12-16

Subduction zones modulate the chemical evolution of the Earth's mantle. Water and volatile elements in the slab are released as fluids into the mantle wedge and this process is widely considered to result in the oxidation of the sub-arc mantle. However, the chemical composition and speciation of these fluids, which is critical for the mobility of economically important elements, remain poorly constrained. Sulfur has the potential to act both as oxidizing agent and transport medium. Here we use zinc stable isotopes (δ 66 Zn) in subducted Alpine serpentinites to decipher the chemical properties of slab-derived fluids. We show that the progressive decrease in δ 66 Zn with metamorphic grade is correlated with a decrease in sulfur content. As existing theoretical work predicts that Zn-SO 4 2- complexes preferentially incorporate heavy δ 66 Zn, our results provide strong evidence for the release of oxidized, sulfate-rich, slab serpentinite-derived fluids to the mantle wedge.

The Luanchuan Mo-W-Pb-Zn-Ag magmatic-hydrothermal system in the East Qinling metallogenic belt, China: Constrains on metallogenesis from C-H-O-S-Pb isotope compositions and Rb-Sr isochron ages

NASA Astrophysics Data System (ADS)

Cao, Hua-Wen; Zhang, Shou-Ting; Santosh, M.; Zheng, Luo; Tang, Li; Li, Dong; Zhang, Xu-Huang; Zhang, Yun-Hui

2015-11-01

The Luanchuan Mo-W-Pb-Zn-Ag polymetallic ore district is located in the East Qinling metallogenic belt on the southern margin of the North China Craton. Two ore fields (Nannihu and Yuku) are recognized in the district, and three types of deposits are identified from the two ore fields as follows: (1) the 6 proximal porphyry-skarn type Mo-W deposits occurring at the inner contact zone of the granite porphyries, (2) the 3 middle skarn-hydrothermal type Zn deposits, and (3) the 8 distal hydrothermal type Pb-Zn-Ag deposits at the periphery of the porphyry. We present C-H-O isotope compositions of hydrothermal quartz and calcite, S-Pb isotope compositions of sulfide minerals, and sphalerite Rb-Sr isochron ages from the 17 deposits. The geochemical and geochronological data from the two ore fields all show systematic temporal and spatial variation, and primarily lead to the following inferences. (1) The temperatures and salinities of the ore-forming fluids decreased during mineralization. The ore-forming fluids gradually evolved from magmatic water to mixed magmatic-meteoric water. (2) The metallogenic components were primarily derived from igneous rocks, with increasing proportions of the materials from the ore-bearing rocks. (3) The mineralization ages of these deposits are close (147-136 Ma), which correspond to the emplacement of the granite intrusions. (4) The three types of deposits and the ore-related late Mesozoic intrusives constitute a unified magmatic-hydrothermal-mineralization system. Finally, we also suggest exploration strategies for the Luanchuan ore district.

Copper and Zinc isotope composition of CR, CB and CH-like meteorites.

NASA Astrophysics Data System (ADS)

Russell, S.; Zhu, X.; Guo, Y.; Mullane, E.; Gounelle, M.; Mason, T.; Coles, B.

2003-04-01

Copper and zinc isotopes have recently been shown to be variable in isotopic composi-tion among terrestrial and extraterrestrial materials [1-3]. For this study, we have se-lected samples (bulk meteorite and chondrule separates) from the CR meteorite clan: Bencubbin (CB), Renazzo (CR2), NWA 801 (CR2), and HaH237 (CH-like). These meteorites were selected because meteorites from this clan have experienced very little alteration since their initial formation [4] and for their extremely high refrac-tory/volatile element ratios. The latter characteristic may allow a test of the correlation observed by [2] between element ratios and Cu isotope composition. Measurements were performed on NHM/IC Micromass Isoprobe and Oxford Nu MC-ICP-MS using techniques described elsewhere [1,5]. Each of the meteorites measured so far for Cu and Zn are isotopically light compared to the terrestrial mantle. This suggests that the terrestrial value may have been altered from the pristine solar system value, or else there were multiple early solar system components. Zinc isotopic com-positions lie on a fractionation line and range from δ66ZnNIST = -1.4±0.1ppm (bulk NWA801) to -1.9±0.1ppm (separated chondrule, NWA 801). Copper isotope compositions vary from δ65CuNIST976 = -1.5±0.1ppm (bulk Renazzo) to -3.1±0.1ppm (separated chondrule, NWA 801). Two chondrules from NWA 801 have differing Cu isotope values (-3.1±0.1 and -2.0±0.1ppm) and both are lighter than the bulk meteorite (-1.9±0.1ppm), suggesting a lack of equilibration with respect to Cu in this meteorite. The light values for the two separated chondrules, compared the bulk meteorite, hints that chondrules may be isotopically lighter than co-existing matrix, metal and sulphides with respect to Cu. The copper isotope compositions are not as isotopically light as expected for the high refractory/volatile element ratio observed in these chondrites. Thus a model to account for the Cu isotopes in chondrites may require greater com-plexity than one involving simple mixing of two primordial components. References: [1] Zhu et al., Chem. Geol. 163,139-149 (2000). [2] Luck et al., GCA 67 143 (2002). [3] Luck et al., MAPS 35 A100 (2000) [4] Krot et al., MAPS 37 1451-1490 (2002) [5] Mason et al. EOS Trans. AGU abstract V21A-0966 82 (2001)

Instrumentation effects on U and Pu CBNM standards spectra quality measured on a 500 mm3 CdZnTe and a 2×2 inch LaBr3 detectors

NASA Astrophysics Data System (ADS)

Meleshenkovskii, I.; Borella, A.; Van der Meer, K.; Bruggeman, M.; Pauly, N.; Labeau, P. E.; Schillebeeckx, P.

2018-01-01

Nowadays, there is interest in developing gamma-ray measuring devices based on the room temperature operated medium resolution detectors such as semiconductor detectors of the CdZnTe type and scintillators of the LaBr3 type. This is true also for safeguards applications and the International Atomic Energy Agency (IAEA) has launched a project devoted to the assessment of medium resolution gamma-ray spectroscopy for the verification of the isotopic composition of U and Pu bearing samples. This project is carried out within the Non-Destructive Assay Working Group of the European Safeguards Research and Development Association (ESARDA). In this study we analyze medium resolution spectra of U and Pu standards with the aim to develop an isotopic composition determination algorithm, particularly suited for these types of detectors. We show how the peak shape of a CdZnTe detector is influenced by the instrumentation parameters. The experimental setup consisted of a 500 mm3 CdZnTe detector, a 2×2 inch LaBr3 detector, two types of measurement instrumentation - an analogue one and a digital one, and a set of certified samples - a 207Bi point source and U and Pu CBNM standards. The results of our measurements indicate that the lowest contribution to the peak asymmetry and thus the smallest impact on the resolution of the 500 mm3 CdZnTe detector was achieved with the digital MCA. Analysis of acquired spectra allowed to reject poor quality measurement runs and produce summed spectra files with the least impact of instrumentation instabilities. This work is preliminary to further studies concerning the development of an isotopic composition determination algorithm particularly suited for CZT and LaBr3 detectors for safeguards applications.

Isotopic insights into biological regulation of zinc in contaminated systems

USGS Publications Warehouse

Wanty, Richard B.; Balistrieri, Laurie S.; Wesner, Jeff S.; Walters, David; Schmidt, Travis S.; Podda, Francesca; De Giudici, G.; Stricker, Craig A.; Kraus, Johanna M.; Lattanzi, Pierfranco; Wolf, Ruth E.; Cidu, R.

2015-01-01

Aquatic organisms use a variety of biogeochemical reactions to regulate essential and non-essential trace metals. Many of these mechanisms can lead to isotopic fractionation, thus measurement of metal isotopes may yield insights into the processes by which organisms respond to metal exposure. We illustrate these concepts with two case studies, one involving an intra- and the other an extra-cellular mechanism of Zn sequestration. In the first study, the mayfly Neocloeon triangulifer was grown in the laboratory, and fed a diet of Zn-doped diatoms at Zn levels exceeding the requirements for normal mayfly life functions. The N. triangulifer larvae consumed the diatoms and retained their Zn isotopic signature. Upon metamorphosis, the subimago life stage lost Zn mass either in the exuvia or by excretion, and the Zn retained was isotopically enriched. Thus, Zn uptake is nonfractionating, but Zn regulation favors the lighter isotope. Thus the Zn remaining in the subimago was isotopically heavier. In the second study, Zn was adsorbed on the cell walls and exopolysaccharide secretions of cyanobacteria, which favored the heavier Zn isotope. Continued adsorption eventually resulted in nucleation and biomineralization of hydrozincite {Zn5(CO3)2(OH)6}. These case studies demonstrate the utility of Zn isotopes to provide insights into how aquatic insects respond to metal exposure.

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.

Heterogeneous distribution of Zn stable isotopes in mice and applications to medical sciences

NASA Astrophysics Data System (ADS)

Moynier, F.; Fujii, T.; Shaw, A.; Le Borgne, M.

2013-12-01

Zinc is required for the function of more than 300 enzymes involved in many metabolic pathways, and is a vital micronutrient for living organisms. To investigate if Zn isotopes could be used to better understand metal homeostasis, as well as a biomarker for diseases, we assessed the distribution of natural Zn isotopes in various mouse tissues. We found that, with respect to Zn isotopes, most mouse organs are isotopically distinct and that the total range of variation within one mouse encompasses the variations observed in the Earth's crust. Therefore, biological activity must have a major impact on the distribution of Zn isotopes in inorganic materials. The most striking aspect of the data is that red blood cells and bones are enriched by ~0.5 per mil in 66Zn relative to 64Zn when compared to serum, and up to ~1 per mil when compared to the brain and liver. This fractionation is well explained by the equilibrium distribution of isotopes between different bonding environments of Zn in different organs. Differences in gender and genetic background did not appear to affect the isotopic distribution of Zn. Together, these results suggest that potential use of Zn isotopes as a tracer for dietary Zn, and for detecting disturbances in Zn metabolism due to pathological conditions.

The behavior of iron and zinc stable isotopes accompanying the subduction of mafic oceanic crust: A case study from Western Alpine ophiolites

NASA Astrophysics Data System (ADS)

Inglis, Edward C.; Debret, Baptiste; Burton, Kevin W.; Millet, Marc-Alban; Pons, Marie-Laure; Dale, Christopher W.; Bouilhol, Pierre; Cooper, Matthew; Nowell, Geoff M.; McCoy-West, Alex J.; Williams, Helen M.

2017-07-01

Arc lavas display elevated Fe3+/ΣFe ratios relative to MORB. One mechanism to explain this is the mobilization and transfer of oxidized or oxidizing components from the subducting slab to the mantle wedge. Here we use iron and zinc isotopes, which are fractionated upon complexation by sulfide, chloride, and carbonate ligands, to remark on the chemistry and oxidation state of fluids released during prograde metamorphism of subducted oceanic crust. We present data for metagabbros and metabasalts from the Chenaillet massif, Queyras complex, and the Zermatt-Saas ophiolite (Western European Alps), which have been metamorphosed at typical subduction zone P-T conditions and preserve their prograde metamorphic history. There is no systematic, detectable fractionation of either Fe or Zn isotopes across metamorphic facies, rather the isotope composition of the eclogites overlaps with published data for MORB. The lack of resolvable Fe isotope fractionation with increasing prograde metamorphism likely reflects the mass balance of the system, and in this scenario Fe mobility is not traceable with Fe isotopes. Given that Zn isotopes are fractionated by S-bearing and C-bearing fluids, this suggests that relatively small amounts of Zn are mobilized from the mafic lithologies in within these types of dehydration fluids. Conversely, metagabbros from the Queyras that are in proximity to metasediments display a significant Fe isotope fractionation. The covariation of δ56Fe of these samples with selected fluid mobile elements suggests the infiltration of sediment derived fluids with an isotopically light signature during subduction.

Early Archean serpentine mud volcanoes at Isua, Greenland, as a niche for early life.

PubMed

Pons, Marie-Laure; Quitté, Ghylaine; Fujii, Toshiyuki; Rosing, Minik T; Reynard, Bruno; Moynier, Frederic; Douchet, Chantal; Albarède, Francis

2011-10-25

The Isua Supracrustal Belt, Greenland, of Early Archean age (3.81-3.70 Ga) represents the oldest crustal segment on Earth. Its complex lithology comprises an ophiolite-like unit and volcanic rocks reminiscent of boninites, which tie Isua supracrustals to an island arc environment. We here present zinc (Zn) isotope compositions measured on serpentinites and other rocks from the Isua supracrustal sequence and on serpentinites from modern ophiolites, midocean ridges, and the Mariana forearc. In stark contrast to modern midocean ridge and ophiolite serpentinites, Zn in Isua and Mariana serpentinites is markedly depleted in heavy isotopes with respect to the igneous average. Based on recent results of Zn isotope fractionation between coexisting species in solution, the Isua serpentinites were permeated by carbonate-rich, high-pH hydrothermal solutions at medium temperature (100-300 °C). Zinc isotopes therefore stand out as a pH meter for fossil hydrothermal solutions. The geochemical features of the Isua fluids resemble the interstitial fluids sampled in the mud volcano serpentinites of the Mariana forearc. The reduced character and the high pH inferred for these fluids make Archean serpentine mud volcanoes a particularly favorable setting for the early stabilization of amino acids.

The giant Upper Yangtze Pb-Zn province in SW China: Reviews, new advances and a new genetic model

NASA Astrophysics Data System (ADS)

Zhou, Jia-Xi; Xiang, Zhen-Zhong; Zhou, Mei-Fu; Feng, Yue-Xing; Luo, Kai; Huang, Zhi-Long; Wu, Tao

2018-04-01

In the western margin of the Yangtze Block, SW China, the Emeishan large igneous province (ELIP) is spatially associated with >400 carbonate-hosted epigenetic Pb-Zn deposits. These deposits form the giant Upper Yangtze Pb-Zn metallogenic province with >20 Mt base metals. In the southeastern part of this province, the important Pb-Zn deposits include those of the Yinchangpo, Yunluhe, Maozhachang, Tianqiao, Banbanqiao, Mangdong, Shaojiwan, Liangyan, Qingshan, Shanshulin, Nayongzhi and Guanziyao deposits. Sulfide ore bodies in these deposits are (i) hosted in late Ediacaran to middle Permian limestone, dolomitic limestone and dolostone; (ii) structurally controlled by reverse fault-anticline tectonic systems; and (iii) spatially associated with the ELIP flood basalts and mafic dikes, and early Permian, early Carboniferous and early Cambrian organic matter-rich black shales. C-O isotopic compositions suggest that dolostone and limestone, mantle-derived rocks of the ELIP, and sedimentary organic matters supplied C-O to the hydrothermal systems through water/rock (W/R) interaction. New and existing S isotopic compositions of sulfides imply multiple sources of S and the reduction of sulfate through both abiotic thermochemical (TSR) and bacterially mediated (BSR) processes. Zn isotopes indicate that the sources of Zn were most likely related to the ELIP with various contributions from sediments and basements locally. Pb isotope signatures are suggestive of derivation of Pb from basements and sedimentary rocks with variable influences from the ELIP. Sr isotopes support that mantle-derived rocks, sediments and basements were involved in Pb-Zn mineralization, and they have various contributions in different deposits. We consider that the Pb-Zn deposits in the Upper Yangtze province are the mixed products of multiple S species-bearing solutions and metal-rich fluids, both of which were derived from, flowed through or interacted with multiple lithostratigraphic units in the western Yangtze Block. The change of tectonic regimes from extension to compression after eruption of basalts of the ELIP, and then to extension during Early Mesozoic, facilitated extraction, migration, and excretion of ore-forming metals and associated fluids. Mixing of fluids and reduction geochemical barrier activated TSR, causing cyclical carbonate dissolution, CO2 degassing and recrystallization (namely carbonate buffer). All these processes triggered continuous precipitation of huge amounts of hydrothermal minerals. Underplating and eruption of ELIP basalts provided heat flow, fluids and volatiles, whereas the basalts acted as an impermeable and protective layer, and even as ore-hosting rocks. These Pb-Zn deposits have spatial and genetic association with igneous activities of the ELIP, and are characterized by high ore grades (>10 wt% Pb + Zn), high concentrations of associated metals (e.g. Cu, Ag, Ge, and Cd), and medium-low temperatures (usually < 300 °C) and salinities (commonly < 20 wt% NaCl equiv.), all of which are significantly different from those of typical Mississippi Valley-type (MVT) deposits. Hence, the carbonate-hosted epigenetic Pb-Zn deposits in the Upper Yangtze metallogenic province representing to a new type of Pb-Zn deposits that are hosted in platform carbonate sequences and formed within compressional zones of passive margin tectonic settings.

Origin of the Red Dog Zn-Pb-Ag deposits, Brooks Range, Alaska: Evidence from regional Pb and Sr isotope sources

USGS Publications Warehouse

Ayuso, R.A.; Kelley, K.D.; Leach, D.L.; Young, L.E.; Slack, J.F.; Wandless, G.; Lyon, A.M.; Dillingham, J.L.

2004-01-01

Pb and Sr isotope data were obtained on the shale-hosted Zn-Pb-Ag Red Dog deposits (Qanaiyaq, Main, Aqqaluk, and Paalaaq), other shale-hosted deposits near Red Dog, and Zn-Pb-Ag sulfide and barite deposits in the western and central Brooks Range. The Red Dog deposits and other shale-hosted Zn-Pb-Ag deposits near Red Dog are hosted in the Mississippian Kuna Formation, which is underlain by a sequence of marine-deltaic clastic rocks of the Upper Devonian to Lower Mississippian Endicott Group. Ag-Pb-Zn vein-breccias are found in the Endicott Group. Galena formed during the main mineralization stages in the Red Dog deposits and from the Anarraaq and Wulik deposits have overlapping Pb isotope compositions in the range 206Pb/204Pb = 18.364 to 18.428, 207Pb/204Pb = 15.553 to 15.621, and 208Pb/204Pb = 38.083 to 38.323. Galena and sphalerite formed during the main ore-forming stages in the Red Dog deposits define a narrow field on standard uranogenic and thorogenic Pb isotope diagrams. Lead in sulfides of the Red Dog district is less radiogenic (238U/204Pb: ?? = 9.51-9.77) than is indicated by the average crustal lead evolution model (?? = 9.74), a difference consistent with a long history of evolution at low ratios of ?? before the Carboniferous. The homogeneous regional isotopic reservoir of Pb may indicate large-scale transport and leaching of minerals with various ?? ratios and Th/Pb ratios. Younger and genetically unrelated fluids did not significantly disturb the isotopic compositions of galena and sphalerite after the main mineralization event in the Red Dog district. Some pyrite shows evidence of minor Pb remobilization. The overall lead isotope homogeneity in the shale-hosted massive sulfide deposits is consistent with three types of control: a homogeneous regional source, mixing of lead during leaching of a thick sedimentary section and fluid transport, or mixing at the site of deposition. Isotopic variability of the hydrothermal fluids, as represented by galena in the Red Dog district, appears to be consistent with a simple mixing system. Evidence indicates that galena was deposited from largely similar hydrothermal solutions throughout the Red Dog district. A shared regional isotopic reservoir is also supported by the correspondence of Pb isotope compositions of galena in deposits of the Red Dog district and galena in clastic rocks (vein-breccias). Leaching of metals and progressive extraction of radiogenic lead from the clastic rocks in the Endicott Group may account for the trend of increasing 206Pb/204Pb in galena of the Red Dog district. Galena in the Red Dog deposits is unlikely to have been derived entirely from the same isotopic reservoir as that represented by the lead in the Kuna Formation or from the igneous rocks in the Red Dog district. Sr isotope data for barite, calcite, and witherite from the Red Dog deposits are compared with data from regional barite that is associated with sulfides and from barite in sulfide-poor occurrences. Fluids with heterogeneous Sr isotope signatures are indicated. Barite in the Main deposit extends to higher ratios of 87Sr/86Sr (0.709034-0.709899) than barite in the Anarraaq deposit (0.708615-0.709256). All barite is more radiogenic than Carboniferous seawater. Other Mississippian(?) shale-hosted deposits and mineral occurrences containing barite in the Red Dog district and barite in regional occurrences east of Red Dog in the western and central Brooks Range also have heterogeneous 87Sr/86Sr ratios. Carbonate (87Sr/86Sr = 0.710319-0.713637) and witherite (87 Sr/86 Sr = 0.710513) in the Main deposit are more radiogenic than barite. In contrast, carbonate (87Sr/86Sr = 0.708196-0.709740) intergrown with massive sulfides at Anarraaq has isotopic compositions similar to that of barite. Paragenetic and isotop ic studies suggest that early barite is similar to barite typically formed in cold seeps along continental margins. This early fine-grained barite formed before the main mineralizat

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).

Nonspecific uptake and homeostasis drive the oceanic cadmium cycle

NASA Astrophysics Data System (ADS)

Horner, Tristan J.; Lee, Renee B. Y.; Henderson, Gideon M.; Rickaby, Rosalind E. M.

2013-02-01

The global marine distributions of Cd and phosphate are closely correlated, which has led to Cd being considered as a marine micronutrient, despite its toxicity to life. The explanation for this nutrient-like behavior is unknown because there is only one identified biochemical function for Cd, an unusual Cd/Zn carbonic anhydrase. Recent developments in Cd isotope mass spectrometry have revealed that Cd uptake by phytoplankton causes isotopic fractionation in the open ocean and in culture. Here we investigate the physiochemical pathways that fractionate Cd isotopes by performing subcellular Cd isotope analysis on genetically modified microorganisms. We find that expression of the Cd/Zn carbonic anhydrase makes no difference to the Cd isotope composition of whole cells. Instead, a large proportion of the Cd is partitioned into cell membranes with a similar direction and magnitude of Cd isotopic fractionation to that seen in surface seawater. This observation is well explained if Cd is mistakenly imported with other divalent metals and subsequently managed by binding within the cell to avoid toxicity. This process may apply to other divalent metals, whereby nonspecific uptake and subsequent homeostasis may contribute to elemental and isotopic distributions in seawater, even for elements commonly considered as micronutrients.

Zinc isotope evidence for sulfate-rich fluid transfer across subduction zones

PubMed Central

Pons, Marie-Laure; Debret, Baptiste; Bouilhol, Pierre; Delacour, Adélie; Williams, Helen

2016-01-01

Subduction zones modulate the chemical evolution of the Earth's mantle. Water and volatile elements in the slab are released as fluids into the mantle wedge and this process is widely considered to result in the oxidation of the sub-arc mantle. However, the chemical composition and speciation of these fluids, which is critical for the mobility of economically important elements, remain poorly constrained. Sulfur has the potential to act both as oxidizing agent and transport medium. Here we use zinc stable isotopes (δ66Zn) in subducted Alpine serpentinites to decipher the chemical properties of slab-derived fluids. We show that the progressive decrease in δ66Zn with metamorphic grade is correlated with a decrease in sulfur content. As existing theoretical work predicts that Zn-SO42− complexes preferentially incorporate heavy δ66Zn, our results provide strong evidence for the release of oxidized, sulfate-rich, slab serpentinite-derived fluids to the mantle wedge. PMID:27982033

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.

The Cd and Zn Isotope Compositions of PM10 in the Atmosphere of Paris: New Tools for Discrimination and Tracking of the Origin of Metallic Pollution

NASA Astrophysics Data System (ADS)

Petelet-Giraud, E.; Widory, D.; Innocent, C.; Quetel, C.; Le Bihan, O.; Fraboulet, I.; Forti, L.; Joos, E.; Goupil, G.; Canard, E.

2008-12-01

Due to their relatively high concentration in urban environments (from 10 to more than 50 μg.m-3), atmospheric particles (PM10) have potential damaging effects on the Public Health. Hence, the development of measures dealing with fine particulate matter is considered a priority by the EU Clean Air For Europe (CAFE) Program. Still, the origin of these airborne particles is subject to debate, as classical chemical methods showed their limitations. Recent studies have shown that stable isotopes of elements such as carbon, nitrogen or lead could be of great help in the search of new particle air pollution tracking tools. We will present here preliminary results on the pioneer use of stable isotope compositions of cadmium, zinc and mercury to help decipher the different possible origins of PM10 pollution in the atmosphere of Paris (France). Main potential sources were characterized: (1) waste incineration, (2) road traffic, (3) central heating and (4) coal-fired power plants. Results show that the use of cadmium (d114Cd) and zinc (d66Zn) isotopes, and the combination of both provides a reliable and precise tool for discriminating the different families of particle vectors. The isotope systematic of mercury (d200Hg) is more difficult to apprehend due to the low levels encountered (mercury is mainly present under gaseous form, but is still observed at low concentrations in particles), but does show significant variations between the different sources. Daily cumulative air samples were taken on three different locations, covering different scenarios in Paris city: 1) background pollution in Paris, 2) under the plume of a major pollution source and 3) Paris vicinity. Corresponding chemical and isotope analyses help identify the main vectors for the three elements (Cd, Zn and Hg) considered as well as assess their respective contributions to the levels of pollution observed.

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.

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.

The oceanic budgets of nickel and zinc isotopes: the importance of sulfidic environments as illustrated by the Black Sea

PubMed Central

Little, Susan H.; Archer, Corey; Cameron, Vyllinniskii; Andersen, Morten B.; Rijkenberg, Micha J. A.; Lyons, Timothy W.

2016-01-01

Isotopic data collected to date as part of the GEOTRACES and other programmes show that the oceanic dissolved pool is isotopically heavy relative to the inputs for zinc (Zn) and nickel (Ni). All Zn sinks measured until recently, and the only output yet measured for Ni, are isotopically heavier than the dissolved pool. This would require either a non-steady-state ocean or other unidentified sinks. Recently, isotopically light Zn has been measured in organic carbon-rich sediments from productive upwelling margins, providing a potential resolution of this issue, at least for Zn. However, the origin of the isotopically light sedimentary Zn signal is uncertain. Cellular uptake of isotopically light Zn followed by transfer to sediment does not appear to be a quantitatively important process. Here, we present Zn and Ni isotope data for the water column and sediments of the Black Sea. These data demonstrate that isotopically light Zn and Ni are extracted from the water column, probably through an equilibrium fractionation between different dissolved species followed by sequestration of light Zn and Ni in sulfide species to particulates and the sediment. We suggest that a similar, non-quantitative, process, operating in porewaters, explains the Zn data from organic carbon-rich sediments. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’. PMID:29035259

Li-Zn-Pb multi isotopic characterization of the Loire River Basin, France

NASA Astrophysics Data System (ADS)

Millot, R.; Desaulty, A.; Widory, D.; Bourrain, X.

2013-12-01

The Loire River in France is approximately 1010 km long and drains an area of 117 800 km2. Upstream, the Loire River flows following a south to north direction from the Massif Central down to the city of Orléans, 650 km from its source. The Loire River is one of the main European riverine inputs to the Atlantic Ocean. Over time, its basin has been exposed to numerous sources of anthropogenic metal pollutions, such as metal mining, industry, agriculture and domestic inputs. The Loire River basin is thus an excellent study site to develop new isotope systematics for tracking anthropogenic sources of metal pollutions (Zn and Pb) and also to investigate Li isotope tracing that can provide key information on the nature of weathering processes at the Loire River Basin scale. Preliminary data show that Li-Zn-Pb concentrations and isotopic compositions span a wide range in river waters of the Loire River main stream and the main tributaries. There is a clear contrast between the headwaters upstream and rivers located downstream in the lowlands. In addition, one of the major tributaries within the Massif Central (the Allier River) is clearly influenced by inputs resulting from mineralizations and thermomineral waters. The results showed that, on their own, each of these isotope systematics reveals important information about the geogenic or anthropogenic origin Li-Zn-Pb. Considered together, they are however providing a more integrated understanding of the overall budgets of these elements at the scale of the Loire River Basin.

Sulfur Isotopic Composition of Sulfides in Skarn and Vein Mineralization of the Dal'negorsk Ore Region (Primorye)

NASA Astrophysics Data System (ADS)

Rogulina, L. I.; Moiseenko, V. G.; Odarichenko, E. G.; Voropayeva, E. N.

2018-03-01

The S isotopic composition in the ore-forming minerals galena and sphalerite was studied in different Ag-Pb-Zn deposits of the region. It was pointed out that the δ34S modal values range from-1.2 to +6.7‰ in the minerals with a positive value for the skarn mineralization. In the flyschoid formation, the vein-type mineralization is characterized by negative and positive values. The narrow range of δ34S values indicates the marginal-continental type of the mineralization and the multiple origins of its sources.

Zinc and Its Isotopes in the Loire River Basin, France

NASA Astrophysics Data System (ADS)

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

2014-12-01

The contribution of human activities such as industries, agriculture and domestic inputs, becomes more and more significant in the chemical composition of the dissolved load of rivers. Human factors act as a supplementary key process. Therefore the mass-balance for the budget of catchments and river basins include anthropogenic disturbances. The Loire River in central France is approximately 1010 km long and drains an area of 117,800 km2. In the upper basin, the bedrock is old plutonic rock overlain by much younger volcanic rocks. The intermediate basin includes three major tributaries flowing into the Loire River from the left bank: the Cher, the Indre and the Vienne rivers; the main stream flows westward and its valley stretches toward the Atlantic Ocean. Here, the Loire River drains the sedimentary series of the Paris Basin, mainly carbonate deposits. The lower Loire basin drains pre-Mesozoic basement of the Armorican Massif and its overlying Mesozoic to Cenozoic sedimentary deposits. The Loire River is one of the main European riverine inputs to the Atlantic ocean. Here we are reporting concentration and isotope data for Zn in river waters and suspended sediments from the Loire River Basin. In addition, we also report concentration and isotope data for the different industrial sources within the Loire Basin, as well as data for biota samples such as mussels and oysters from the Bay of Biscay and North Brittany. These organisms are known to be natural accumulators of metal pollutants. Zinc isotopic compositions are rather homogeneous in river waters with δ66Zn values ranging from 0.21 to 0.39‰. This range of variation is very different from anthropogenic signature (industrial and/or agriculture release) that displays δ66Zn values between 0.02 to 0.14‰. This result is in agreement with a geogenic origin and the low Zn concentrations in the Loire River Basin (from 0.8 to 6 µg/L).

Zinc isotope and transition-element dynamics accompanying hydrozincite biomineralization in the Rio Naracauli, Sardinia, Italy

USGS Publications Warehouse

Wanty, Richard B.; Podda, F.; De Giudici, Giovanni; Cidu, R.; Lattanzi, Pierfranco

2013-01-01

The Rio Naracauli in SW Sardinia drains part of the Ingurtosu Zn–Pb mining district, and contains extreme concentrations of dissolved Zn at near-neutral pH. In the upper reaches of the stream, pH, alkalinity and Zn concentrations are such that hydrozincite [Zn5(CO3)2(OH)6] precipitates in a biologically mediated process facilitated by a microalga (Chlorella sp.) and a cyanobacterium (Scytonema sp.). Values of δ66Zn in water and solid samples ranged from − 0.35‰ to + 0.5‰ relative to the JMC 3-0749-Lyon standard, and closely follow a mass-dependent fractionation line. Two composite samples of sphalerite, the primary ore mineral in the Ingurtosu deposits, had an average δ66Zn of + 0.15‰, similar to sphalerite measured elsewhere in hydrothermal mineral deposits. Zinc isotope measurements of the stream water and the hydrozincite forming in the stream show a consistent preference for the heavy isotope, 66Zn, in the hydrozincite relative to 64Zn. Synthetic hydrozincites produced without added bacteria have δ66Zn identical to the dissolved Zn, thus suggesting a biologically mediated mineralization process in Rio Naracauli. The average fractionation, Δhdz-water, is 0.35‰, the magnitude of which is consistent with other studies, and suggests an extracellular mechanism of the biomineralization process. Zinc concentration and dissolved δ66Zn steadily decrease in the reach of the stream where the biomineralization occurs. The biomineralization process also leads to the sequestration of Pb, Cu and Ni in the hydrozincite lattice, and the coeval precipitation of an amorphous CdCO3 solid, prompting the suggestion that if optimized, the biomineralization process might represent a feasible passive remediation strategy for streams with high Zn and other metals, and with near-neutral pH.

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.

Early Archean serpentine mud volcanoes at Isua, Greenland, as a niche for early life

PubMed Central

Pons, Marie-Laure; Quitté, Ghylaine; Fujii, Toshiyuki; Rosing, Minik T.; Reynard, Bruno; Moynier, Frederic; Douchet, Chantal; Albarède, Francis

2011-01-01

The Isua Supracrustal Belt, Greenland, of Early Archean age (3.81–3.70 Ga) represents the oldest crustal segment on Earth. Its complex lithology comprises an ophiolite-like unit and volcanic rocks reminiscent of boninites, which tie Isua supracrustals to an island arc environment. We here present zinc (Zn) isotope compositions measured on serpentinites and other rocks from the Isua supracrustal sequence and on serpentinites from modern ophiolites, midocean ridges, and the Mariana forearc. In stark contrast to modern midocean ridge and ophiolite serpentinites, Zn in Isua and Mariana serpentinites is markedly depleted in heavy isotopes with respect to the igneous average. Based on recent results of Zn isotope fractionation between coexisting species in solution, the Isua serpentinites were permeated by carbonate-rich, high-pH hydrothermal solutions at medium temperature (100–300 °C). Zinc isotopes therefore stand out as a pH meter for fossil hydrothermal solutions. The geochemical features of the Isua fluids resemble the interstitial fluids sampled in the mud volcano serpentinites of the Mariana forearc. The reduced character and the high pH inferred for these fluids make Archean serpentine mud volcanoes a particularly favorable setting for the early stabilization of amino acids. PMID:22006301

Zinc isotope fractionation during adsorption onto Mn oxyhydroxide at low and high ionic strength

NASA Astrophysics Data System (ADS)

Bryan, Allison L.; Dong, Shuofei; Wilkes, Elise B.; Wasylenki, Laura E.

2015-05-01

Marine ferromanganese sediments represent one of the largest sinks from global seawater for Zn, a critical trace metal nutrient. These sediments are variably enriched in heavier isotopes of Zn relative to deep seawater, and some are among the heaviest natural samples analyzed to date. New experimental results demonstrate that adsorption of Zn to poorly crystalline Mn oxyhydroxide results in preferential association of heavier isotopes with the sorbent phase. At low ionic strength our experimental system displayed a short-lived kinetic isotope effect, with light isotopes adsorbed to birnessite (Δ66/64Znadsorbed-dissolved ∼ -0.2‰). After 100 h the sense of fractionation was opposite, such that heavier isotopes were preferentially adsorbed at steady state, but the magnitude of Δ66/64Znadsorbed-dissolved was indistinguishable from zero (+0.05 ± 0.08‰). At high ionic strength, we observed preferential sorption of heavy isotopes, with a strong negative correlation between Δ66/64Znadsorbed-dissolved and the percentage of Zn on the birnessite. Values of Δ66/64Znadsorbed-dissolved ranged from nearly +3‰ at low surface loading to +0.16‰ at high surface loading. Based on previous EXAFS work we infer that Zn adsorbs first as tetrahedral, inner-sphere complexes at low surface loading, with preferential incorporation of heavier isotopes relative to the octahedral Zn species predominating in solution. As surface loading increases, so does the proportion of Zn adsorbing as octahedral complexes, thus diminishing the magnitude of fractionation between the dissolved and adsorbed pools of Zn. The magnitude of fractionation at high ionic strength is also governed by aqueous speciation of Zn in synthetic seawater; a substantial fraction of Zn ions reside in chloro complexes, which preferentially incorporate light Zn isotopes, and this drives the adsorbed pool to be heavier relative to the bulk solution than it was at low ionic strength. Our results explain the observation that ferromanganese sediments are enriched in heavier isotopes of Zn relative to deep seawater. This represents a step towards building a robust mass balance model for Zn isotopes in the oceans and potentially using Zn isotopes to trace biogeochemical cycling of this important element in the modern and ancient oceans.

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.

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).

Application of iron and zinc isotopes to track the sources and mechanisms of metal loading in a mountain watershed

USGS Publications Warehouse

Borrok, D.M.; Wanty, R.B.; Ian, Ridley W.; Lamothe, P.J.; Kimball, B.A.; Verplanck, P.L.; Runkel, R.L.

2009-01-01

Here the hydrogeochemical constraints of a tracer dilution study are combined with Fe and Zn isotopic measurements to pinpoint metal loading sources and attenuation mechanisms in an alpine watershed impacted by acid mine drainage. In the tested mountain catchment, ??56Fe and ??66Zn isotopic signatures of filtered stream water samples varied by ???3.5??? and 0.4???, respectively. The inherent differences in the aqueous geochemistry of Fe and Zn provided complimentary isotopic information. For example, variations in ??56Fe were linked to redox and precipitation reactions occurring in the stream, while changes in ??66Zn were indicative of conservative mixing of different Zn sources. Fen environments contributed distinctively light dissolved Fe (<-2.0???) and isotopically heavy suspended Fe precipitates to the watershed, while Zn from the fen was isotopically heavy (>+0.4???). Acidic drainage from mine wastes contributed heavier dissolved Fe (???+0.5???) and lighter Zn (???+0.2???) isotopes relative to the fen. Upwelling of Fe-rich groundwater near the mouth of the catchment was the major source of Fe (??56Fe ??? 0???) leaving the watershed in surface flow, while runoff from mining wastes was the major source of Zn. The results suggest that given a strong framework for interpretation, Fe and Zn isotopes are useful tools for identifying and tracking metal sources and attenuation mechanisms in mountain watersheds. ?? 2009 Elsevier Ltd.

Dynamics of Zn in an urban wetland soil-plant system: Coupling isotopic and EXAFS approaches

NASA Astrophysics Data System (ADS)

Aucour, Anne-Marie; Bedell, Jean-Philippe; Queyron, Marine; Magnin, Valérie; Testemale, Denis; Sarret, Géraldine

2015-07-01

Plants play a key role in the stabilization of metals in contaminated environments. Studies have been performed on Zn uptake and storage mechanisms, mainly for Zn hyperaccumulating plants, though less is known about Zn stabilization in the rhizosphere of non-accumulating plants. This study was focused on the dynamics of Zn in a whole soil-litter-plant system and the processes controlling Zn mobilization and stabilization. The site studied was an infiltration basin receiving urban stormwater, in which Phalaris arundinacea (reed canary grass) developed spontaneously. A combination of chemical extractions (CaCl2, DTPA), EXAFS spectroscopy and Zn stable isotope measurements was applied for the water inlet, soil, plant organs and decaying biomass. Zn speciation changed from the water inlet to the soil. In the soil, Zn was present as Zn-layered double hydroxide (Zn-LDH), tetrahedral and octahedral sorbed Zn species. The formation of Zn-LDH participates in Zn stabilization. Tetrahedral Zn species, which were partly DTPA exchangeable, were enriched in heavy isotopes, whereas octahedral Zn (Zn-LDH and sorbed species) were enriched in light isotopes. Based on a linear model between δ66Zn and Zn speciation, δ66Zn for pure tetrahedral and octahedral end-members were estimated at ca. 0.33‰ and 0.04‰, respectively. In the plant, a mixture of octahedral Zn (attributed to aqueous Zn-organic acid complexes present in the symplasm), and tetrahedral Zn (attributed to apoplasmic Zn-cell wall complexes) was observed in all organs. Large enrichment in light isotopes from the soil to the plant Δ66Zn (of ca. -0.6‰) was observed. The stem was enriched in light isotopes versus roots and, to a lesser extent, versus leaves. The results suggest that Zn was taken up via a low-affinity transport system and that Zn was sequestrated in the stem symplasm after transit through leaves. Finally, intense Zn exchanges were observed between the decaying biomass and the soil, with the sorption of heavy Zn from the soil to cell wall remains and release of light Zn to the soil. Overall, this study provides a complete overview of Zn cycling in an urban wetland soil-plant system, and describes several changes in Zn speciation with Zn isotopic fractionation processes in a complex system.

Antimony isotopic composition in river waters affected by ancient mining activity.

PubMed

Resongles, Eléonore; Freydier, Rémi; Casiot, Corinne; Viers, Jérôme; Chmeleff, Jérôme; Elbaz-Poulichet, Françoise

2015-11-01

In this study, antimony (Sb) isotopic composition was determined in natural water samples collected along two hydrosystems impacted by historical mining activities: the upper Orb River and the Gardon River watershed (SE, France). Antimony isotope ratio was measured by HG-MC-ICP-MS (Hydride Generation Multi-Collector Inductively Coupled Plasma Mass Spectrometer) after a preconcentration and purification step using a new thiol-cellulose powder (TCP) procedure. The external reproducibility obtained for δ(123)Sb measurements of our in-house Sb isotopic standard solution and a certified reference freshwater was 0.06‰ (2σ). Significant isotopic variations were evident in surface waters from the upper Orb River (-0.06‰≤δ(123)Sb≤+0.11‰) and from the Gardon River watershed (+0.27‰≤δ(123)Sb≤+0.83‰). In particular, streams that drained different former mining sites exploited for Sb or Pb-Zn exhibited contrasted Sb isotopic signature, that may be related to various biogeochemical processes occurring during Sb transfer from rocks, mine wastes and sediments to the water compartment. Nevertheless, Sb isotopic composition appeared to be stable along the Gardon River, which might be attributed to the conservative transport of Sb at distance from mine-impacted streams, due to the relative mobile behavior of Sb(V) in natural oxic waters. This study suggests that Sb isotopic composition could be a useful tool to track pollution sources and/or biogeochemical processes in hydrologic systems. Copyright © 2015 Elsevier B.V. All rights reserved.

Zn isotope study of atmospheric emissions and dry depositions within a 5 km radius of a Pb-Zn refinery

NASA Astrophysics Data System (ADS)

Mattielli, Nadine; Petit, Jérôme C. J.; Deboudt, Karine; Flament, Pascal; Perdrix, Esperanza; Taillez, Aurélien; Rimetz-Planchon, Juliette; Weis, Dominique

The present paper examines the use of zinc isotopes as tracers of atmospheric sources and focuses on the potential fractionation of Zn isotopes through anthropogenic processes. In order to do so, Zn isotopic ratios are measured in enriched ores and airborne particles associated with pyrometallurgical activities of one of the major Pb-Zn refineries in France. Supporting the isotopic investigation, this paper also compares morphological and chemical characteristics of Zn particles collected on dry deposition plates ("environmental samples") placed within a 5 km radius of the smelter, with those of Zn particles collected inside the plant ("process samples"), i.e. dust collected from the main exhaust system of the plant. To ensure a constant isotopic "supply", the refinery processed a specific set of ores during the sampling campaigns, as agreed with the executive staff of the plant. Enriched ores and dust produced by the successive Zn extraction steps show strong isotope fractionation (from -0.66 to +0.22‰) mainly related to evaporation processes within the blast furnaces. Dust from the main chimney displays a δ 66Zn value of -0.67‰. Application of the Rayleigh equation to evaluate the fractionation factor associated with the Zn vapor produced after a free evaporation gives a range of αore/vapor from 1.0004 to 1.0008. The dry deposits, collected on plates downwind of the refinery, display δ 66Zn variations of up to +0.7‰. However, it is to be noted that between 190 and 1250 m from the main chimney of the refinery, the dry deposits show a high level of large (>10 μm) Zn, S, Fe and O bearing aggregates characterized by positive δ 66Zn values (+0.02 to +0.19‰). These airborne particles probably derive from the re-suspension of slag heaps and local emissions from the working-units. In contrast, from 1720 to 4560 m, the dry deposits are comprised of small (PM10) particles, including spherical Zn-bearing aggregates, showing negative δ 66Zn values (-0.52 to -0.02‰). Our results suggest that the source of the distal dry fallouts is the main chimney plume, whose light Zn isotopic signature they preserve. Based on Zn isotopic analysis in combination with morphological and chemical characteristics of airborne particles, the present study suggests the traceability of smelter dusts by Zn isotopes.

Synthesis of isotopically modified ZnO nanoparticles and their potential as nanotoxicity tracers

USGS Publications Warehouse

Dybowska, A.D.; Croteau, M.-N.; Misra, S.K.; Berhanu, D.; Luoma, S.N.; Christian, P.; O'Brien, P.; Valsami-Jones, E.

2011-01-01

Understanding the behavior of engineered nanoparticles in the environment and within organisms is perhaps the biggest obstacle to the safe development of nanotechnologies. Reliable tracing is a particular issue for nanoparticles such as ZnO, because Zn is an essential element and a common pollutant thus present at elevated background concentrations. We synthesized isotopically enriched (89.6%) with a rare isotope of Zn (67Zn) ZnO nanoparticles and measured the uptake of 67Zn by L. stagnalis exposed to diatoms amended with the particles. Stable isotope technique is sufficiently sensitive to determine the uptake of Zn at an exposure equivalent to lower concentration range (<15 ??g g-1). Without a tracer, detection of newly accumulated Zn is significant at Zn exposure concentration only above 5000 ??g g-1 which represents some of the most contaminated Zn conditions. Only by using a tracer we can study Zn uptake at a range of environmentally realistic exposure conditions. ?? 2010 Elsevier Ltd. All rights reserved.

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.

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.

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.

Lead-isotopic, sulphur-isotopic, and trace-element studies of galena from the Silesian-Cracow Zn-Pb ores, polymetallic veins from the Gory Swietokrzyskie MTS, and the Myszkow porphyry copper deposit, Poland

USGS Publications Warehouse

Church, S.E.; Vaughn, R.B.; Gent, C.A.; Hopkins, R.T.

1996-01-01

Lead-isotopic data on galena samples collected from a paragenetically constrained suite of samples from the Silesian-Cracow ore district show no regional or paragenetically controlled lead-isotopic trends within the analytical reproducibility of the measurements. Furthermore, the new lead-isotopic data agree with previously reported lead-isotopic results (R. E. Zartman et al., 1979). Sulfur-isotopic analyses of ores from the Silesian-Cracow district as well as from vein ore from the Gory Swietokrzyskie Mts. and the Myszkow porphyry copper deposit, when coupled with trace-element data from the galena samples, clearly discriminate different hydrothermal ore-forming events. Lead-isotopic data from the Permian and Miocene evaporite deposits in Poland indicate that neither of these evaporite deposits were a source of metals for the Silesian-Cracow district ores. Furthermore, lead-isotopic data from these evaporite deposits and the shale residues from the Miocene halite samples indicate that the crustal evolution of lead in the central and western European platform in southern Poland followed normal crustal lead-isotopic growth, and that the isotopic composition of crustal lead had progressed beyond the lead-isotopic composition of lead in the Silesian-Cracow ores by Permian time. Thus, Mesozoic and Tertiary sedimentary flysch rocks can be eliminated as viable source rocks for the metals in the Silesian-Cracow Mississippi Valley-type (MVT) deposits. The uniformity of the isotopic composition of lead in the Silesian-Cracow ores, when coupled with the geologic evidence that mineralization must post-date Late Jurassic faulting (E. Gorecka, 1991), constrains the geochemical nature of the source region. The source of the metals is probably a well-mixed, multi-cycle molasse sequence of sedimentary rocks that contains little if any Precambrian metamorphic or granitic clasts (S. E. Church, R. B. Vaughn, 1992). If ore deposition was post Late Jurassic (about 150 m. y.) or later as indicated by the geologic evidence, the source rocks probably contained elevated concentrations of Zn and Pb (75-100 ppm), and relatively low concentrations of U and Th (2 and 8 ppm or less, respectively). The Carboniferous coal-bearing molasse rocks of the Upper Silesian Coal Basin are a prime candidate for such a source region. The presence of ammonia and acetate in the fluid inclusions (Viets et al., 1996a) also indicate that the Carboniferous coal-bearing molasse sequence in the Upper Silesian Coal Basin may have been a suitable pathway for the MVT ore fluids. The lead-isotopic homogeneity, when coupled with the sulfur-isotopic heterogeneity of the ores suggests that mixing of a single metal-bearing fluid with waters from separate aquifers containing variable sulfur-isotopic compositions in karsts in the Muschelkalk Formation of Middle Triassic age may have been responsible for the precipitation of the ores of the Silesian-Cracow district.

Zinc isotope investigation of surface and pore waters in a mountain watershed impacted by acid rock drainage.

PubMed

Aranda, Suzan; Borrok, David M; Wanty, Richard B; Balistrieri, Laurie S

2012-03-15

The pollution of natural waters with metals derived from the oxidation of sulfide minerals like pyrite is a global environmental problem. However, the metal loading pathways and transport mechanisms associated with acid rock drainage reactions are often difficult to characterize using bulk chemical data alone. In this study, we evaluated the use of zinc (Zn) isotopes to complement traditional geochemical tools in the investigation of contaminated waters at the former Waldorf mining site in the Rocky Mountains, Colorado, U.S.A. Geochemical signatures and statistical analysis helped in identifying two primary metal loading pathways at the Waldorf site. The first was characterized by a circumneutral pH, high alkalinity, and high Zn/Cd ratios. The second was characterized by acidic pHs and low Zn/Cd ratios. Zinc isotope signatures in surface water samples collected across the site were remarkably similar (the δ(66)Zn, relative to JMC 3-0749-L, for most samples ranged from 0.20 to 0.30‰±0.09‰ 2σ). This probably suggests that the ultimate source of Zn is consistent across the Waldorf site, regardless of the metal loading pathway. The δ(66)Zn of pore water samples collected within a nearby metal-impacted wetland area, however, were more variable, ranging from 0.20 to 0.80‰±0.09‰ 2σ. Here the Zn isotopes seemed to reflect differences in groundwater flow pathways. However, a host of secondary processes might also have impacted Zn isotopes, including adsorption of Zn onto soil components, complexation of Zn with dissolved organic matter, uptake of Zn into plants, and the precipitation of Zn during the formation of reduced sulfur species. Zinc isotope analysis proved useful in this study; however, the utility of this isotopic tool would improve considerably with the addition of a comprehensive experimental foundation for interpreting the complex isotopic relationships found in soil pore waters. Copyright © 2012 Elsevier B.V. All rights reserved.

Spatial evolution of Zn-Fe-Pb isotopes of sphalerite within a single ore body: A case study from the Dongshengmiao ore deposit, Inner Mongolia, China

NASA Astrophysics Data System (ADS)

Gao, Zhaofu; Zhu, Xiangkun; Sun, Jian; Luo, Zhaohua; Bao, Chuang; Tang, Chao; Ma, Jianxiong

2018-01-01

Analyses of sphalerite minerals from the characteristic brecciated Zn-Pb ores of the main ore body in the giant Dongshengmiao deposit have revealed variations in δ66Zn from 0.17 to 0.40‰ and in δ56Fe from -1.78 to -0.35‰. Further, the investigated pyrrhotite samples have iron that is isotopically similar to that of associated sphalerite minerals. The most distinctive pattern revealed by the zinc and iron isotope data is the lateral trend of increasing δ66Zn and δ56Fe values from southwest to northeast within the main ore body. The lead isotopic homogeneity of ore sulfides from the main ore body suggests that there is only one significant source for metal, thus precluding the mixing of multiple metal sources as the key factor controlling spatial variations of zinc and iron isotopes. The most likely control on spatial variations is Rayleigh fractionation during hydrothermal fluid flow, with lighter Zn and Fe isotopes preferentially incorporated into the earliest sulfides to precipitate from fluids. Precipitations of sphalerite and pyrrhotite have played vital roles in the Zn and Fe isotopic variations, respectively, of the ore-forming system. Accordingly, the larger isotopic variability for Fe than Zn within the same hydrothermal system perhaps resulted from a larger proportion of precipitation for pyrrhotite than for sphalerite. The lateral trend pattern revealed by the zinc and iron isotope data is consistent with the occurrence of a cystic-shaped breccia zone, which is characterized by marked elevation in Cu. The results further confirm that Zn and Fe isotopes can be used as a vectoring tool for mineral prospecting.

Bioavailability and uptake of smelter emissions in freshwater zooplankton in northeastern Washington, USA lakes using Pb isotope analysis and trace metal concentrations.

PubMed

Child, A W; Moore, B C; Vervoort, J D; Beutel, M W

2018-07-01

The upper Columbia River and associated valley systems are highly contaminated with metal wastes from nearby smelting operations in Trail, British Columbia, Canada (Teck smelter), and to a lesser extent, Northport, Washington, USA (Le Roi smelter). Previous studies have investigated depositional patterns of airborne emissions from these smelters, and documented the Teck smelter as the primary metal contamination source. However, there is limited research directed at whether these contaminants are bioavailable to aquatic organisms. This study investigates whether smelter derived contaminants are bioavailable to freshwater zooplankton. Trace metal (Zn, Cd, As, Sb, Pb and Hg) concentrations and Pb isotope compositions of zooplankton and sediment were measured in lakes ranging from 17 to 144 km downwind of the Teck smelter. Pb isotopic compositions of historic ores used by both smelters are uniquely less radiogenic than local geologic formations, so when zooplankton assimilate substantial amounts of smelter derived metals their compositions deviate from local baseline compositions toward ore compositions. Sediment metal concentrations and Pb isotope compositions in sediment follow significant (p < 0.001) negative exponential and sigmoidal patterns, respectively, as distance from the Teck smelting operation increases. Zooplankton As, Cd, and Sb contents were related to distance from the Teck smelter (p < 0.05), and zooplankton Pb isotope compositions suggest As, Cd, Sb and Pb from historic and current smelter emissions are biologically available to zooplankton. Zooplankton from lakes within 86 km of the Teck facility display isotopic evidence that legacy ore pollution is biologically available for assimilation. However, without water column data our study is unable to determine if legacy contaminants are remobilized from lake sediments, or erosional pathways from the watershed. Copyright © 2018 Elsevier Ltd. All rights reserved.

Iron and zinc isotope fractionation during uptake and translocation in rice (Oryza sativa) grown in oxic and anoxic soils

NASA Astrophysics Data System (ADS)

Arnold, Tim; Markovic, Tamara; Kirk, Guy J. D.; Schönbächler, Maria; Rehkämper, Mark; Zhao, Fangjie J.; Weiss, Dominik J.

2015-11-01

Stable isotope fractionation is emerging quickly as a powerful novel technique to study metal uptake and translocation in plants. Fundamental to this development is a thorough understanding of the processes that lead to isotope fractionation under differing environmental conditions. In this study, we investigated Zn and Fe isotope fractionation in rice grown to maturity in anaerobic and aerobic soils under greenhouse conditions. The overall Zn isotope fractionation between the soil and above ground plant material was negligible in aerobic soil but significant in anaerobic soil with isotopically lighter Zn in the rice plant. The observed range of fractionation is in line with previously determined fractionations of Zn in rice grown in hydroponic solutions and submerged soils and emphasizes the effect of taking up different chemical forms of Zn, most likely free and organically complexed Zn. The Zn in the grain was isotopically lighter than in the rest of the above ground plant in rice grown in aerobic and anaerobic soils alike. This suggests that in the course of the grain loading and during the translocation within the plant important biochemical and/or biophysical processes occur. The isotope fractionation observed in the grains would be consistent with an unidirectional controlled transport from shoot to grain with a fractionation factor of α ≈ 0.9994. Iron isotopes showed an isotopic lighter signature in shoot and grain compared to the bulk soil or the leachate in aerobic and anaerobic soils alike. The negative direction of isotopic fractionation is consistent with possible changes in the redox state of Fe occurring during the uptake and translocation processes. The isotope fractionation pattern between shoots and grain material are different for Zn and Fe which finally suggests that different mechanisms operate during translocation and grain-loading in rice for these two key micronutrients.

Hercynian Pb-Zn mineralization types in the Alcudia Valley mining district (Spain) and their reflect in Pb isotopic signatures

NASA Astrophysics Data System (ADS)

García de Madinabeitia, S.; Santos Zalduegui, J. F.; Palero, F.; Gil Ibarguchi, J. I.; Carracedo, M.

2003-04-01

More than 450 ore deposits indexed within the Alcudia Valley of the Central-Iberian Zone (Spain) may be grouped by their tectonic and lithologic characteristics (1,2) as follows: type A of rare stratabound mineralizations, and types B, C, D and E represented by abundant Hercynian veins (post-Namurian). 86 new Pb isotope analyses of galenas from the four vein types reveal that types B and C have similar isotopic ratios with values of μ_2 = 10.07, ω_2 = 40.6 and a mean model age of 564 Ma. Types D and E have μ_2 and ω_2 values of 9.79 and 38.5, respectively, but differ each other with respect to their model ages, 600 Ma (type D) and 335 Ma (type E). The observed variations appear to be related to the geochemical features of the metasedimentary host-rocks of the mineralizations where two distinct types of Pb isotopic ratios have been reported (3): one with μ_2 and ω_2 comparable to those of the D and E types and another with a more radiogenic composition, close to those of the B and C types of galenas. Nägler et al. have suggested partial rehomogeneization of Pb isotopic composition within the metasediments at ca. 330 Ma, that is, prior to the mineralization events, but the extent of this process and its effects on the ore bodies isotopic features is not evident. The origin of the more abundant E type ore bodies has been related to the Hercynian granitic rocks in the area (2, and references therein). Other plutons within this sector of the Central Iberian Zone (e.g., Linares, etc.; cf. accompanying Abstract) associate ore bodies whose Pb isotopic composition is very similar to that of the E type galenas from the Alcudia Valley. The isotopic data obtained thus point to a related or common source material for the various types of granites within the area studied. Yet, the Pb isotopic composition of other mineralizations (B, C, D), likewise located in Hercynian veins, allow to consider different types of Pb-Zn ore bodies and point therefore to different sources of Pb at a regional scale. (1) Palero, F.J. Ph. D., University of Salamanca, Spain (1991). (2) Palero, F.; Both, R.A.; Arribas, A.; Boyce, A.J.; Mangas, J. &Martín-Izard, A. Economic Geology (in press). (3) Nägler, T. Ph. D., Diss ETH, Zurich N^o 9245 (1990).

The Marine Biogeochemistry of Zinc Isotopes

DTIC Science & Technology

2007-06-01

hydrothermal fluids and minerals, cultured marine phytoplankton, natural plankton, and seawater. By measuring Zn isotopes in a diverse array of...variations were discovered in hydrothermal fluids and minerals, with hydrothermal fluids ranging in 6 66Zn from 0.02 %o to +0.93 %o, and chimney minerals...drives much of the Zn isotope fractionation in hydrothermal systems. In cultured diatoms, a relationship was discovered between Zn transport by

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.

Using combinations of metal isotopes as tracers of tailings pond discharges to subsurface aquifers in the Athabasca Oil Sands area, Canada.

NASA Astrophysics Data System (ADS)

Gammon, P. R.; Savard, M. M.; Ahad, J. M.; Girard, I.

2016-12-01

The Athabasca Oil Sands (AOS) industry in Alberta, Canada deposits voluminous waste streams in Earth's largest tailings ponds (TPs). Detecting and tracing contaminant discharge from TPs to subsurface aquifers has proven difficult because tailings have the same composition as the surrounding environment of unmined oil sand. To trace pond discharge to the subsurface therefore relies on the waste stream hosting additions or alterations induced by mining or industrial processes. Inorganic element or contaminant concentration data have proven ineffective at tracing because there is insufficient alteration of the chemical constituents or their ratios. Metal isotopes have not generally been applied to tracing emissions even though isotopic fractionation is likely induced via the high temperature and pH industrial process. We have generated Mg, Li, Pb and Zn isotopic data for a range of groundwater wells and TPs. Mg isotopes are excellent for distinguishing deep saline brines that are pumped into the waste stream during mine dewatering. Li isotopes appear to be heavily fractionated during processing, which produces a heavy isotopic signature that is an excellent tracer of production water. Pb isotopes discriminate Pb derived from oil-sand versus bedrock carbonate. Juxtapositions of TPs, carbonates and near-surface aquifers are common and of significant regulatory concern, making Pb isotopes particularly useful. Zn isotopic data indicates similarities to Pb isotopes, but are difficult to obtain due to low concentrations. Combining the isotopic data with concentration data and hydrologic models will assist in determining the fluxes of discharges from the TPs to near-surface aquifers. The range of environmental contexts of AOS TPs is limited and thus monitoring discharges to nearby aquifers from TPs could feasibly be accomplished using tailored suites of metal isotopes.

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.

Constraints of C-O-S isotope compositions and the origin of the Ünlüpınar volcanic-hosted epithermal Pb-Zn ± Au deposit, Gümüşhane, NE Turkey

NASA Astrophysics Data System (ADS)

Akaryali, Enver; Akbulut, Kübra

2016-03-01

The Eastern Pontide Orogenic Belt (EPOB) constitutes one of the best examples of the metallogenic provinces in on the Alpine-Himalayan belt. This study focuses on the genesis of the Ünlüpınar Pb-Zn ± Au deposit in the southern part of the Eastern Pontide Orogenic Belt. The main lithological units in the study area are the Early Carboniferous Kurtoğlu Metamorphic Complex the Late Carboniferous Köse Granitoid and the Early-Middle Jurassic Şenköy Formation. The studied deposit is hosted by the Şenköy Formation, which consists predominantly of basaltic-andesitic rocks and associated pyroclastic rocks that are calc-alkaline in composition. Silicic, sulfidic, argillic, chloritic, hematitic, carbonate and limonite are the most obvious alteration types observed in the deposit site. Ore microscopy studies exhibit that the mineral paragenesis in deposits includes pyrite, chalcopyrite, sphalerite, galena, gold, quartz and calcite. Electron microprobe analyses conducted on sphalerite indicate that the Zn/Cd ratio varies between 84 and 204, and these ratios point at a hydrothermal deposit related to granitic magmas. Fluid inclusion studies in calcite and quartz show that the homogenization temperature of the studied deposit ranges between 90-160 °C and 120-330 °C respectively. The values of sulfur isotope analysis of pyrite, sphalerite and galena minerals vary between 1.6‰ and 5.7‰, and the results of oxygen and carbon isotope analysis range between 8.4‰ and 18‰ and -5‰ and -3.6‰, respectively. The average formation temperature of the ore was calculated as 264 °C with a sulfur isotope geothermometer. All of the data indicate that the Ünlüpınar deposit is an epithermal vein-type mineralization that was formed depending on the granitic magmatism.

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

Jamieson-Hanes, Julia H.; Shrimpton, Heather K.; Veeramani, Harish

A flow-through cell experiment was conducted to evaluate Zn isotope fractionation during ZnS precipitation under microbially-mediated sulfate-reducing conditions. Synthetic groundwater containing 0.90 mM Zn was pumped through a cell containing creek sediment that was biostimulated to promote sulfate reducing conditions. Real-time, in situ X-ray absorption spectroscopy (XAS) was applied at the Zn K-edge to collect spectra via a Kapton® window in the front of the cell over the course of the experiment. Aqueous effluent samples were collected and analysed to determine concentrations of anions and cations, and Zn isotope ratios. The flow rate was increased step-wise during the experiment tomore » modify the residence time and produce changes in the extent of sulfate reduction, which in turn controlled the extent of ZnS precipitation. Greater enrichment in the heavier isotope in the aqueous phase relative to the input solution was associated with more extensive Zn removal. A Rayleigh curve was fit to the isotope data, where ε = -0.27 ± 0.06‰ (2σ). Evaluation of Zn isotope fractionation under controlled flow conditions is critical to improve the efficacy of this powerful analytical technique when applied to natural systems or remediation projects in the field.« less

The Abundance and Isotopic Composition of Hg in Extraterrestrial Materials

NASA Technical Reports Server (NTRS)

Lauretta, D. S.

2004-01-01

During the past three year grant period we made excellent progress in our study of the abundances and isotopic compositions of Hg and other volatile trace elements in extraterrestrial materials. As part of my startup package I received funds to construct a state-of-the-art experimental facility to study gas-solid reaction kinetics. Much of our effort was spent developing the methodology to measure the abundance and isotopic composition of Hg at ultratrace levels in solid materials. In our first study, the abundance and isotopic composition of Hg was determined in bulk samples of the Murchison (CM) and Allende (CV) carbonaceous chondrites. We have continued our study of mercury in primitive meteorites and expanded the suite of meteorites to include other members of the CM and CV chondrite group as well as CI and CO chondrites. Samples of the CI chondrite Orgueil, the CM chondrites Murray, Nogoya, and Cold Bokkeveld, the CO chondrites Kainsaz, Omans, and Isna, and the CV chondrites Vigarano, Mokoia, and Grosnaja were tested. We have developed a thermal analysis ICP-MS technique and applied it to the study of a suite of thermally labile elements (Zn, As, Se, Cd, In, Sn, Sb, Te, Hg, Au, Tl, Pb, and Bi) in geologic materials as well.

The Balmat-Edwards zinc-lead deposits-synsedimentary ore from Mississippi valley-type fluids.

USGS Publications Warehouse

Whelan, J.F.; Rye, R.O.; Delorraine, W.

1984-01-01

The Balmat-Edwards Zn-Pb district in New York is in Mid-Proterozoic Grenville marbles. Tabular to podiform, generally conformable massive sphalerite-galena orebodies occur at various horizons in the approx 1 km-thick marbles. Metamorphism obscured or obliterated most primary characteristics, whose reconstruction is attempted through detailed S, C, and O isotope studies of the Fowler orebody, and trace element and S isotope studies of sphalerite concentrates and composite ore samples from 22 orebodies. Sulphur isotope data reflect equilibration at near peak metamorphism with some indication of re-equilibration during retrograde metamorphism. The carbon and oxygen isotope composition of gangue carbonates suggests derivation from the host marbles. The oxygen isotope composition of gangue quartz is compatible with a chert origin or metamorphism-equilibration with other minerals. Sulphur and lead isotopes and sulphide mineralogy suggests that the ore fluids were evolved basin brines, chemically like those responsible for Mississippi Valley-type deposits. The large stratigraphic span (> 600 m) of the Balmat orebodies may be due to basin dewatering of million-year intervals. Stratigraphically increasing 34S values of evaporite-anhydrite are postulated to record hydrothermal events and to imply bacterial sulphate reduction on an unusually large scale. Such a stratigraphic increase may be a general exploration guide where sediment-hosted exhalative deposits or Mississippi Valley-type deposits occur.-G.J.N.

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.

Zinc isotope ratios of bones and teeth as new dietary indicators: results from a modern food web (Koobi Fora, Kenya)

NASA Astrophysics Data System (ADS)

Jaouen, Klervia; Beasley, Melanie; Schoeninger, Margaret; Hublin, Jean-Jacques; Richards, Michael P.

2016-05-01

In order to explore the possibilities of using zinc (Zn) stable isotope ratios as dietary indicators, we report here on the measurements of the ratio of stable isotopes of zinc (66Zn/64Zn, expressed here as δ66Zn) in bioapatite (bone and dental enamel) of animals from a modern food web in the Koobi Fora region of the Turkana Basin in Kenya. We demonstrate that δ66Zn values in both bone and enamel allow a clear distinction between carnivores and herbivores from this food web. Differences were also observed between browsers and grazers as well as between carnivores that consumed bone (i.e. hyenas) compared to those that largely consume flesh (i.e. lions). We conclude that Zn isotope ratio measurements of bone and teeth are a new and promising dietary indicator.

Contrasting isotopic signatures between anthropogenic and geogenic Zn and evidence for post-depositional fractionation processes in smelter-impacted soils from Northern France

NASA Astrophysics Data System (ADS)

Juillot, Farid; Maréchal, Chloe; Morin, Guillaume; Jouvin, Delphine; Cacaly, Sylvain; Telouk, Philipe; Benedetti, Marc F.; Ildefonse, Philippe; Sutton, Steve; Guyot, François; Brown, Gordon E., Jr.

2011-05-01

Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ 66Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2 σ) to +0.34 ± 0.17‰ (2 σ) at the lowest horizons and from +0.38 ± 0.45‰ (2 σ) to +0.76 ± 0.14‰ (2 σ) near the surface. The δ 66Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ 66Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe 2O 4)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ 66Zn values of +0.81 ± 0.20‰ (2 σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ 66Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ 66Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.

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.

Two mineralization events in the Baiyinnuoer Zn-Pb deposit in Inner Mongolia, China: Evidence from field observations, S-Pb isotopic compositions and U-Pb zircon ages

NASA Astrophysics Data System (ADS)

Jiang, Si-Hong; Chen, Chun-Liang; Bagas, Leon; Liu, Yuan; Han, Ning; Kang, Huan; Wang, Ze-Hai

2017-08-01

The Xing-Mong Orogenic Belt (XMOB) is located in the eastern part of the Central Asian Orogenic Belt (CAOB) and has experienced multiple tectonic events. The Baiyinnuoer Pb-Zn deposit may be a rare case that documents two periods of mineralization in the tectonically complex XMOB. There are two types of Pb-Zn mineralization in the deposit: (1) skarn-type ore, hosted by the skarn in the contact zone between marble and granodiorite and within the marble and (2) vein-type ore, hosted by crystal tuff and feldspar porphyry. This study revealed that the host rocks, mineral assemblages, mineralization occurrences, S-Pb isotopes, and ages between the two types of ore are notably different. Zircon U-Pb dating indicates that the granodiorite was emplaced in the Early Triassic (244 ± 1 to 242 ± 1 Ma), the crystal tuff was deposited in the Early Cretaceous (140 ± 1 to 136 ± 1 Ma), and the feldspar porphyry was intruded in the Early Cretaceous (138 ± 2 to 136 ± 2 Ma). The first skarn mineralization occurred at ∼240 Ma and the second vein-type Pb-Zn mineralization took place between 136 and 129 Ma. Thus the Triassic orebodies were overprinted by Early Cretaceous mineralization. The sphalerite and galena from the skarn mineralization have higher δ34S values (-4.7 to +0.3‰) than the sphalerite, galena and aresenopyrite from the vein-type mineralization (-7.5 to -4.2‰), indicating different sulfur sources or ore-forming processes for the two types of mineralization. The Pb isotopic compositions of the two types of ore are very similar, suggesting similar lead sources. Geochemistry and Nd-Pb-Hf isotopic systematics of the igneous rocks in the region show that the Triassic granodiorite was generated from hybridization of mafic and felsic magmas due to strong crust-mantle interaction under the collisional setting that resulted following the closure of the Paleo-Asian Ocean and the collision of North China and Siberian cratons at the end of the Permian; while the Cretaceous igneous rocks at Baiyinnuoer originated from the partial melting of a juvenile lower crust with minor input from the crust caused by the underplating of mafic magma in an extensional setting.

Evidence for microbial activity in the formation of carbonate-hosted Zn-Pb deposits

NASA Astrophysics Data System (ADS)

Kucha, H.; Raith, J.

2009-04-01

*Kucha H **Raith J *University of Mining and Metallurgy, Faculty of Geology, Geophysics and Environmental Protection, Mickiewicza 30, PL-30-059 Krakow, Poland. ** University of Leoben, Department of Applied Geosciences and Geophysics, A-8700 Leoben, Peter Tunner Str. 5, Austria Evidence for microbial activity in the formation of carbonate-hosted Zn-Pb deposits To date evaluation of bacterial processes in the formation of carbonate-hosted Zn-Pb deposits is largely based on sulphur isotope evidence. However, during a past few years, textural criteria, have been established, which support the bacterial origin of many of these deposits. This has received a strong support from micro-, and nano-textures of naturally growing bacterial films in a flooded tunnel within carbonates that host the Piquette Zn-Pb deposit (Druschel et al., 2002). Bacterial textures, micro- and nano textures found in carbonate-hosted Zn-Pb deposits are: i)wavy bacterial films up to a few mm thick to up to a few cm long composed of peloids, ii)semimassive agglomeration of peloids in the carbonate matrix, and iii)solitary peloids dispersed in the carbonate matrix. Peloids are usually composed of a distinct 50-90um core most often made up of Zn-bearing calcite surrounded by 30-60um thick dentate rim composed of ZnS. Etching of Zn-carbonate cores reveals 1 - 2um ZnS filaments, and numerous 15 to 90nm large ZnS nano-spheres (Kucha et al., 2005). In massive ore composite Zn-calcite - sphalerite peloids are entirely replaced by zinc sulphide, and form peloids ghosts within banded sulphide layers. Bacterially derived micro- and nano-textures have been observed in the following carbonate-hosted Zn-Pb deposits: 1)Irish-type Zn-Pb deposits. In the Navan deposit the basic sulphur is isotopically light bacteriogenic S (Fallick at al., 2001). This is corroborated by semimassive agglomerations of composite peloids (Zn-calcite-ZnS corona or ZnS core-melnikovite corona). Etching of Zn-calcite core reveals globular 0.5 to 1um large fossilised bacteria with some nano-size spheres as well (Kucha et al., 1990). In the Silvermines and Ballinalack ores wavy bacterial film-like textures composed of peloids made up of Zn-calcite or Zn-siderite cores and ZnS rims are known (Kucha et al., 1990). 2) Alpine Zn-Pb deposits. Bleiberg sulphides, Austria, Zn-Pb ores display the δ34S‰ values from -32 to -2 (n=284), with mean close to 20‰ (Schroll & Rantitsch, 2005). Cardita and Crest ores contain wavy bacterial films (-28.84 to -27.91‰). Semimassive globular sphalerite with globules varying in size from 90 to 180um is a basic ZnS type in the Bleiberg ores with light sulphur from (-30.49 to -26.4‰). Based on sulphur isotope data, um-sized bacterial filaments, and spherical nano-textures seen in etched ZnS globules, sulphate reducing bacteria (SRB) involvement is suggested (Kucha et al. 2005). ZnS globules were formed by replacement of original peloids (i.e. bacterial colonies) and/or by agglomeration of original 10-15nm ZnS spheres secreted by SRB. The growth of peloids was promoted by unbalanced electric charges on the surfaces of these ZnS nano-spheres. 3) Upper Silesian MVT Zn-Pb deposits. Sulphur isotopes vary between 2 and 12‰, (mean 5‰) for early stage sulphides, main stage sulphides are characterised by S signature -2 to -15‰. Redeposition of ZnS from the horst to graben structures produced "pulvery" sphalerite with -19‰ (Haranczyk, 1993). Sulphide stalactites containing oxysulphides have δS‰ vales of -23.7. Bacterial microtextures occur mainly within oxysulphides and at the contact between Fe-smithsonite replaced by banded sphalerite (Kucha et al., 1990). 4) La Calamine and Engis, Belgium, contain bacterial micro- and nano-textures in ores related to karst cavities, and paleoweathering crusts (Kucha et al., 1990). The biogenic textures are represented by clumps of peloids, and bacterial mats occurring in banded sphalerite composed of replaced peloids. Peloids are composed of Zn-calcite cores and ZnS rims, oxysulphides, thiosulphates, vaesite and chalcedonic silica. Bacterial microtextures in all of the above mentioned deposits are as a rule associated with oxysulphides i.e. compounds with mixed and intermediate sulphur valences (Kucha et al., 1989). The origin of oxysulphides is probably related either directly to incomplete bacterial reduction of the sulphatic sulphur, or reaction of bacterial H2S with sulphatic S present in the fluids. Some of peloids are composed of oxysulphides (Kucha & Stumpfl, 1992; Kucha, 2003). Therefore, an interpretation of the S isotopic signature of bacterial textures should consider not only microbial community structure, but also the oxidative part of the sulphur cycle proceeding through compounds with mixed sulphur valences. References Druschel GK, Labrenz M, Thomsen-Ebert T, Fowler DA, Banfield JF (2002) Geochemical modelling of ZnS in biofilms: An example of ore depositional processes. Economic Geology, v 97, 1319-1329. Fallick, AE, Ashton JH, Boyce AJ, Ellam RM, Russell MJ (2001) Bacteria were responsible fort he magnitude of the world-class hydrothermal base metal sulphide orebody at Navan, Ireland. Economic Geology, v 96, 885 - 890. Haranczyk Cz (1993) Sulphur isotope models of genesis of the Silesian-Cracov Zn-Pb ore deposits. Geological Quarterly, v 37, 307 - 322. Kucha H (1988) Biogenic and non-biogenic concentration of sulfur and metals in the carbonate-hosted Ballinalack Zn-Pb deposit, Ireland. Min. Pet., 38, 171-187. Kucha H, Wouters R, Arkens O (1989) Determination of sulfur and iron valence by microprobe. Scanning Microscopy, 3, no 1, 89-97. Kucha H, Van der Biest J, Viaene W (1990) Peloids in strata bound Zn-Pb deposits and their genetic importance. Min. Deposita, 25, 132-139. Kucha H, Stumpfl EF (1992) Thiosulphates as precursors of banded sphalerite and pyrite at Bleiberg, Austria. Min. Mag., 56, 165-172. Kucha H (2003) Mississippi Valley Type Zn-Pb deposits of Upper Silesia, Poland, 253-272. In: Kelly, J., G., Andrew, C., J., Ashton, J., H., Boland, M., B., Earls, E., Fusciardi, L., Stanley, G. (eds) Europe's Major Base Metal Deposits, Irish Association for Economic Geology, Printed by Colour Books Ltd, Dublin 2003, 551 pp. Kucha H, Schroll E, Stumpfl EF (2005) Fossil sulphate-reducing bacteria in the Bleiberg lead-zinc deposit, Austria. Mineralium Deposita, v 40, 123-126. Schroll E, Rantitsch G (2005) Sulfur isotope patterns in the Bleiberg deposit (Eastern Alps) and their implications for genetically affiliated. Mineralogy and Petrology 148: 1-18.

The zinc stable isotope signature of waste rock drainage in Arctic Canada

NASA Astrophysics Data System (ADS)

Matthies, Romy; Blowes, David

2014-05-01

Leachate emerging from a pilot-scale waste rock pile of the Diavik diamond mine, Northwest Territories, was monitored. The well-characterized waste rock consists of granite, pegmatitic granite and biotite schist with an average total sulfur and carbonate carbon concentration of 0.053 and 0.027 wt. %, respectively. During the field seasons of 2011 and 2012, the Zn stable isotope footprint was characterized alongside standard monitoring parameters. pH ranged between 4.3 and 6.8 and carbonate alkalinity was low or undetectable. Al and Fe concentrations averaged 6.78 mg L-1 and 175 µg L-1, respectively. The pH and metal mobility were governed by sulfide oxidation and sorption and co-precipitation onto iron and aluminium hydroxides. The main processes controlling zinc mobility in the range of 0.4 and 4.7 mg L-1 was the oxidative dissolution of sphalerite (ZnS) in the biotite schist and the attenuation of zinc onto secondary iron and aluminium hydroxides and desorption upon the pH declining below the pHpzc. The isotope ratios between -0.16 and +0.19 ‰ (δ66Zn, avg = +0.05 ‰, n = 43) are consistent with values reported from other sphalerite containing deposits. Zn isotope ratios and concentrations were largely uncorrelated suggesting that the processes affecting Zn mobility had little or no impact on the Zn isotope signature. Data indicate, that the Zn isotope ratios of the waste rock leachate may be used as a fingerprint to track anthropogenic, mine-derived Zn sources under varying environmental conditions.

Tracking the rise of eukaryotes to ecological dominance with zinc isotopes.

PubMed

Isson, Terry T; Love, Gordon D; Dupont, Christopher L; Reinhard, Christopher T; Zumberge, Alex J; Asael, Dan; Gueguen, Bleuenn; McCrow, John; Gill, Ben C; Owens, Jeremy; Rainbird, Robert H; Rooney, Alan D; Zhao, Ming-Yu; Stueeken, Eva E; Konhauser, Kurt O; John, Seth G; Lyons, Timothy W; Planavsky, Noah J

2018-06-05

The biogeochemical cycling of zinc (Zn) is intimately coupled with organic carbon in the ocean. Based on an extensive new sedimentary Zn isotope record across Earth's history, we provide evidence for a fundamental shift in the marine Zn cycle ~800 million years ago. We discuss a wide range of potential drivers for this transition and propose that, within available constraints, a restructuring of marine ecosystems is the most parsimonious explanation for this shift. Using a global isotope mass balance approach, we show that a change in the organic Zn/C ratio is required to account for observed Zn isotope trends through time. Given the higher affinity of eukaryotes for Zn relative to prokaryotes, we suggest that a shift toward a more eukaryote-rich ecosystem could have provided a means of more efficiently sequestering organic-derived Zn. Despite the much earlier appearance of eukaryotes in the microfossil record (~1700 to 1600 million years ago), our data suggest a delayed rise to ecological prominence during the Neoproterozoic, consistent with the currently accepted organic biomarker records. © 2018 John Wiley & Sons Ltd.

Chemical and boron isotopic composition of tourmaline from the Mariinsky emerald deposit, Central Urals, Russia

NASA Astrophysics Data System (ADS)

Baksheev, Ivan A.; Trumbull, Robert B.; Popov, Mikhail P.; Erokhin, Yuri V.; Kudryavtseva, Olesya E.; Yapaskurt, Vasily O.; Khiller, Vera V.; Vovna, Galina M.; Kiselev, Vladimir I.

2018-04-01

Tourmaline is abundant at the Mariinsky schist-hosted emerald deposit in the Central Urals, Russia, both in emerald-bearing phlogopite veins (type 1) and later, emerald-free pockets, lenses, and veinlets cutting the phlogopite veins (type 2). The Ca content in tourmaline is influenced by the host rocks (ultramafic and mafic rocks), associated minerals, and minerals crystallized before tourmaline (amphibole, fluorite, margarite). The Na concentration in tourmaline depends on the presence or absence of paragonite, and the association with micas also strongly influences the contents of Li, Zn, Ni, and Co in tourmaline. Type 1 tourmalines associated with phlogopite are relatively depleted in these elements, whereas type 2 tourmalines associated with margarite or paragonite are enriched. Some differences in isomorphic substitutions along with the trace element composition (Zn, V, Sr, Co, REE) may have value in exploration of emerald-bearing and emerald-free veins in schist-hosted emerald deposits. The δ11B values in tourmaline of all types fall in a narrow total range from -11.3 to -8.4‰. These values, combined with a mineralization temperature of 420-360 °C, yield an estimated δ11B fluid composition of -7.4 to -6.8‰ suggesting a mixed source of boron, likely dominated from the granitic rocks surrounding the emerald belt. The narrow range of B-isotope compositions in tourmaline from throughout the Mariinsky deposit suggests a well-mixed hydrothermal system.

Zn isotope fractionation in the komatiitic and tholeiitic lava flows of Fred's flow and Theo's flow (Ontario, Canada)

NASA Astrophysics Data System (ADS)

Mattielli, N. D.; Haenecour, P.; Debaille, V.

2010-12-01

Komatiites are subvolcanic or volcanic ultramafic rocks characterized by a high MgO content (>18 wt%) usually but not systematically associated to a spinifex texture. Komatiites are nearly exclusively Archean in age and essentially found in the greenstone belts of the oldest cratons, although some rare Proterozoic and Cretaceous examples are also known. Komatiitic flows are commonly associated with tholeiitic lavas, which have many petrological, textural and geochemical similarities with komatiites. We present new high-precision MC-ICPMS Zinc isotopic data for the komatiitic lavas of Fred’s flow and the associated tholeiitic lavas of Theo’s flow from Munro Township in the 2.7 Ga Abitibi greenstone belt (Ontario, Canada). Zinc isotopes show a significant shift between Fred’s flow (mean δ66Zn = +0.30±0.04‰ (2SD)) and Theo’s flow samples (mean δ66Zn = +0.39±0.03‰ (1)). In addition, the two flows show a systematic shift in δ66Zn between the ultrabasic level at the bottom of the sequence (= +0.51± 0.04‰ and +0.47±0.04‰ for Fred’s Flow and Theo’s Flow, respectively) and the rest of the pile (Δ = 0.21±0.01‰). According to the literature, processes of secondary alteration may cause Zn isotope fractionation. However, petrographic data indicate a slight alteration fingerprint while the geochemical study (whole rock and in-situ) shows no remobilization of HFSE and REE by secondary alteration (low-grade metamorphism and/or hydrothermal alteration). In addition, if similar levels of alteration affected the two lava flows, the alteration process cannot explain the difference of δ66Zn between Fred’s and Theo’s flows. Alternatively, this isotopic difference can be interpreted as reflecting either source effects or mineral fractionation related to spinel crystallization. The correlation between the δ66Zn values and the Cr bulk concentrations may suggest fractionation effects of Zn isotopes by the crystallization of spinel minerals. However, the conditions and the processes implying Zn isotopic fractionation during the crystallization of spinel minerals are still not much studied. Isotopic fractionation related to source effects cannot also be excluded. This latter hypothesis implies that Fred’s flow and Theo’s flow formed from two geochemical or mineralogical different mantle sources. While the geochemical data do not support or invalidate this second hypothesis, two different sources may explain the difference between the two lava flows; however, it cannot account for the isotopic variations observed at the ultrabasic levels. In conclusion, the role of mineralogy either at the origin or during the crystallization evolution should be investigated for a better understanding of Zn isotope fractionation in the mantle. (1): To validate the quality of isotopic analyses, reference materials BCR-1(basalt) (δ66Zn = +0.33±0.03‰) and HRM-27(gabbro) (+0.17±0.01‰) (n=3) have been measured.

Trace Element and Cu Isotopic Tracers of Subsurface Flow and Transport in Wastewater Irrigated Soils

NASA Astrophysics Data System (ADS)

Carte, J.; Fantle, M. S.

2017-12-01

An understanding of subsurface flow paths is critical for quantifying the fate of contaminants in wastewater irrigation systems. This study investigates the subsurface flow of wastewater by quantifying the distribution of trace contaminants in wastewater irrigated soils. Soil samples were collected from the upper 1m of two wetlands at Penn State University's wastewater irrigation site, at which all effluent from the University's wastewater treatment plant has been sprayed since 1983. Major and trace element and Cu isotopic composition were determined for these samples, in addition to wastewater effluent and bedrock samples. The upper 20 cm of each wetland shows an enrichment of Bi, Cd, Cr, Cu, Mo, Ni, Pb, and Zn concentrations relative to deep (>1m) soils at the site by a factor of 1.7-3.5. Each wetland also has a subsurface clay rich horizon with Bi, Cu, Li, Ni, Pb, and Zn concentrations enriched by a factor of 1.4 to 5 relative to deep soils. These subsurface horizons directly underlie intervals that could facilitate preferential effluent flow: a gravel layer in one wetland, and a silty loam with visible mottling, an indication of dynamic water saturation, in the other. Trace metal concentrations in other horizons from both wetlands fall in the range of the deep soils. Significant variability in Cu isotopic composition is present in soils from both wetlands, with δ65Cu values ranging from 0.74‰ to 5.09‰. Soil δ65Cu correlates well with Cu concentrations, with lighter δ65Cu associated with higher concentrations. The Cu isotopic composition of the zones of metal enrichment are comparable to the ostensible average wastewater effluent δ65Cu value (0.61‰), while other horizons have considerably heavier δ65Cu values. We hypothesize that wastewater is the source of the metal enrichments, as each of the enriched elements are present as contaminants in wastewater, and the enrichments are located in clay-rich horizons conducive to trace metal immobilization due to adsorption. This hypothesis will be further tested by modeling with the reactive transport code CrunchTope. This study provides evidence that trace element and isotopic composition of soils can be useful tracers of subsurface hydrologic pathways and elemental fate and transport.

sources and processes identification for Zn cycling in the Seine river, France

NASA Astrophysics Data System (ADS)

gelabert, A.; Jouvin, D.; Morin, G.; Louvat, P.; Guinoiseau, D.; Benedetti, M. F.

2011-12-01

Because the availability of global freshwater stocks is predicted to become a major problem in a near future, new directives on water policy have been established in Europe. As a result, an accurate determination of the ecological status of the Seine river watershed is required. However, important evaluation limitation still exist, partly because the metal cycling in this system is not fully understood with for instance half the Seine river Zn not having clearly identified sources. Recent developments in isotopic measurements for new stable isotopes (Zn, Cu) allow many progresses in understanding the dynamics of metals in natural systems. But this technique alone does not always provide a precise distinction between mixing of water sources and biochemical processes able to induce isotopic fractionation. Along with an isotopic approach, this study propose to use XAS (X-ray Absorption Spectroscopy) to determine precisely the speciation of Zn complexes, and thus to define the proportion of water mixing vs. processes for Zn transfer in the watershed. A geographical sampling transect has been performed downstream Paris. Significant isotopic signature variations have been observed, varying from δ66Zn = 0.04 ± 0.04 to 0.18 ± 0.04 in the particulate part, and from δ66Zn= -0.28 ± 0.04 to 0.08 ± 0.04 for the dissolved part. The XAS analysis performed on the same samples at the Zn K-edge confirmed this heterogeneity by showing different speciations with a major contribution of sulfides, iron oxides and organic ligands. Interestingly, the wastewater treatment plant in Achères constitutes an important location in the system by contributing to the enrichment of heavy Zn to the Seine River particulate material. This change in isotopic signature follows a change in Zn speciation with decrease in sulfides contribution after Achères. A second important location is the confluence between the Seine and a minor river (Epte river) with a significant decrease in the δ66Zn for the particulate part. However, no major changes in Zn speciation have been observed. The cause for this isotopic decrease remains unclear but could be either 1) the mobilization of unknown sources, especially in this area (for the sampling point after the convergence) where the river is connected to numerous small lakes, or 2) the presence of biogeochemical processes able to induce a Zn isotopic fractionation. For instance, microorganisms present in freshwaters are known to be able to fractionate Zn during sorption processes, and they do not necessarily induce a change in the first shells of the Zn complexes if the sorbed metal was previously complexed with organic ligands in the river (fulvic substances with carboxylic or phenolic functional groups for instance). Although additional studies on the Seine river need to be conducted in order to reach a more complete understanding of this watershed functioning, these important results demonstrate the value of combining both the XAS and isotopic approaches in order to understand the behaviour of metals in such complex environments.

A history of violence: Insights into post-accretionary heating in carbonaceous chondrites from volatile element abundances, Zn isotopes and water contents

NASA Astrophysics Data System (ADS)

Mahan, Brandon; Moynier, Frédéric; Beck, Pierre; Pringle, Emily A.; Siebert, Julien

2018-01-01

Carbonaceous chondrites (CCs) may have been the carriers of water, volatile and moderately volatile elements to Earth. Investigating the abundances of these elements, their relative volatility, and isotopes of state-change tracer elements such as Zn, and linking these observations to water contents, provide vital information on the processes that govern the abundances and isotopic signatures of these species in CCs and other planetary bodies. Here we report Zn isotopic data for 28 CCs (20 CM, 6 CR, 1 C2-ung, and 1 CV3), as well as trace element data for Zn, In, Sn, Tl, Pb, and Bi in 16 samples (8 CM, 6 CR, 1 C2-ung, and 1 CV3), that display a range of elemental abundances from case-normative to intensely depleted. We use these data, water content data from literature and Zn isotopes to investigate volatile depletions and to discern between closed and open system heating. Trace element data have been used to construct relative volatility scales among the elements for the CM and CR chondrites. From least volatile to most, the scale in CM chondrites is Pb-Sn-Bi-In-Zn-Tl, and for CR chondrites it is Tl-Zn-Sn-Pb-Bi-In. These observations suggest that heated CM and CR chondrites underwent volatile loss under different conditions to one another and to that of the solar nebula, e.g. differing oxygen fugacities. Furthermore, the most water and volatile depleted samples are highly enriched in the heavy isotopes of Zn. Taken together, these lines of evidence strongly indicate that heated CM and CR chondrites incurred open system heating, stripping them of water and volatiles concomitantly, during post-accretionary shock impact(s).

Evolution of nuclear structure in neutron-rich odd-Zn isotopes and isomers

NASA Astrophysics Data System (ADS)

Wraith, C.; Yang, X. F.; Xie, L.; Babcock, C.; Bieroń, J.; Billowes, J.; Bissell, M. L.; Blaum, K.; Cheal, B.; Filippin, L.; Garcia Ruiz, R. F.; Gins, W.; Grob, L. K.; Gaigalas, G.; Godefroid, M.; Gorges, C.; Heylen, H.; Honma, M.; Jönsson, P.; Kaufmann, S.; Kowalska, M.; Krämer, J.; Malbrunot-Ettenauer, S.; Neugart, R.; Neyens, G.; Nörtershäuser, W.; Nowacki, F.; Otsuka, T.; Papuga, J.; Sánchez, R.; Tsunoda, Y.; Yordanov, D. T.

2017-08-01

Collinear laser spectroscopy was performed on Zn (Z = 30) isotopes at ISOLDE, CERN. The study of hyperfine spectra of nuclei across the Zn isotopic chain, N = 33- 49, allowed the measurement of nuclear spins for the ground and isomeric states in odd-A neutron-rich nuclei up to N = 50. Exactly one long-lived (>10 ms) isomeric state has been established in each 69-79Zn isotope. The nuclear magnetic dipole moments and spectroscopic quadrupole moments are well reproduced by large-scale shell-model calculations in the f5pg9 and fpg9d5 model spaces, thus establishing the dominant term in their wave function. The magnetic moment of the intruder Iπ = 1 /2+ isomer in 79Zn is reproduced only if the νs1/2 orbital is added to the valence space, as realized in the recently developed PFSDG-U interaction. The spin and moments of the low-lying isomeric state in 73Zn suggest a strong onset of deformation at N = 43, while the progression towards 79Zn points to the stability of the Z = 28 and N = 50 shell gaps, supporting the magicity of 78Ni.

Isotopic evidence of spatial magnitude of the Pb deposition near a lead smelter

NASA Astrophysics Data System (ADS)

Flament, P.; Franssens, M.; Debout, K.; Weis, D.

2003-05-01

In order to détermine the dry deposition of lead around a Pb-Zn refinery, two cross-sectional sampling experiments, using deposition plates, have been performed on a daiiy basis, ucder representative meteorological situations (north-easterly and south-westerly winds). The amount of lead deposited as well as its isotopic composition (expressed by the ^{206}Pb/^{207}Pb ratio) are systematically measured. For a daily production of approximately 670 metric tons of (Pb+Zn) the dry fallout, greater than 1000 μg Pb.h^{-1}.m^{-2} on the edge of the plant, falls to about 100 μg Pb.h^{-1}.m^{-2}, four kilometres away from the refinery. This value is still ten times higher than th urban background (<10 μg Pb.h^{-1}.m^{-2}). The spatial extension of the dry deposition plume is evidenced by the evolution of the isotopic signature of the refinery (1.10<^{206}Pb/^{207}), clearly distinct from the urban backgrounde signature (1.15<^{206}Pb/^{207}Pb<1.16). As a first estimate, the extension of the deposition plume seems not to be linked to the wind speed. At the opposite, diffuse emissions from slag heaps are related to this parameter.

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.

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.

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.

Cu Isotopic Composition in Surface Environments and in Biological Systems: A Critical Review

PubMed Central

Wang, Zhuhong; Chen, Jiubin; Zhang, Ting

2017-01-01

Copper (Cu) is a transition metal and an essential micronutrient for organisms, but also one of the most widespread toxic inorganic contaminants at very high content. The research on Cu isotopes has grown rapidly in the last decade. Hitherto, a large number of studies have been published on the theoretical fractionation mechanisms, experimental data and natural variations of Cu isotopes in variable environments and ecosystems. These studies reported a large variation of δ65Cu (−16.49 to +20.04‰) in terrestrial samples and showed that Cu isotopes could be fractionated by various biogeochemical processes to different extent. Several papers have previously reviewed the coupling of Cu and Zn isotope systematics, and we give here a tentative review of the recent publications only on Cu isotopesin variable surface repositories, animals and human beings, with a goal to attract much attention to research on Cu (and other metals) behaviors in the environment and biological systems. PMID:28524094

One century sedimentary record of lead and zinc pollution in Yangzong Lake, a highland lake in southwestern China.

PubMed

Zhang, Enlou; Liu, Enfeng; Shen, Ji; Cao, Yanmin; Li, Yanling

2012-01-01

Reconstruction of trace metal pollution histories and sources may help us to regulate current pollutant discharge. This is especially important for the highland lakes in southwestern China, which are facing trace metals pollution. We present sedimentary records of 11 metals accumulated in Yangzong Lake since the 1870's, a highland lake in southwestern China. Pollution of lead and zinc (Pb and Zn) was differentiated based on principal component analysis, geochemical normalization, and lead isotope ratios. Nearly all the metals as well as grain size composition show generally constant values before the mid-1980's, denoting stable detrital input in the catchment. Fluctuations in the concentrations of the metals as well as grain size composition since the mid-1980's indicate an increase in soil erosion with strengthened human disturbance in the catchment. After geochemical normalization, Pb and Zn showed constant values before 1990 AD and then a gradual increase in parallel with the variations in 208Pb/206Pb and 207Pb/206Pb ratios, indicating that Pb and Zn pollution occurred. Combining the data of 208pb/206Pb and 207Pb/6Pb ratios in the sediments of Yangzong Lake, leaded gasoline, Pb-Zn ore and coal, and consumption or production historical trends, we deduced that the enhanced Pb and Zn pollution in Yangzong Lake is caused primarily by ore mining and refining.

Endogenous Lunar Volatiles

NASA Technical Reports Server (NTRS)

McCubbin, F. M.; Liu, Y.; Barnes, J. J.; Boyce, J. W.; Day, J. M. D.; Elardo, S. M.; Hui, H.; Magna, T.; Ni, P.; Tartese, R.;

Zn/Cd ratios and cadmium isotope evidence for the classification of lead-zinc deposits

PubMed Central

Wen, Hanjie; Zhu, Chuanwei; Zhang, Yuxu; Cloquet, Christophe; Fan, Haifeng; Fu, Shaohong

2016-01-01

Lead-zinc deposits are often difficult to classify because clear criteria are lacking. In recent years, new tools, such as Cd and Zn isotopes, have been used to better understand the ore-formation processes and to classify Pb-Zn deposits. Herein, we investigate Cd concentrations, Cd isotope systematics and Zn/Cd ratios in sphalerite from nine Pb-Zn deposits divided into high-temperature systems (e.g., porphyry), low-temperature systems (e.g., Mississippi Valley type [MVT]) and exhalative systems (e.g., sedimentary exhalative [SEDEX]). Our results showed little evidence of fractionation in the high-temperature systems. In the low-temperature systems, Cd concentrations were the highest, but were also highly variable, a result consistent with the higher fractionation of Cd at low temperatures. The δ114/110Cd values in low-temperature systems were enriched in heavier isotopes (mean of 0.32 ± 0.31‰). Exhalative systems had the lowest Cd concentrations, with a mean δ114/110Cd value of 0.12 ± 0.50‰. We thus conclude that different ore-formation systems result in different characteristic Cd concentrations and fraction levels and that low-temperature processes lead to the most significant fractionation of Cd. Therefore, Cd distribution and isotopic studies can support better understanding of the geochemistry of ore-formation processes and the classification of Pb-Zn deposits. PMID:27121538

Isospin degree of freedom in even-even 68-76Ge and 62-70Zn isotopes

NASA Astrophysics Data System (ADS)

Jalili Majarshin, A.

2018-01-01

The introduction of isotopic spin is significant in light nuclei as Ge and Zn isotopes in order to take into account isospin effects on energy spectra. Dynamical symmetries in spherical, γ-soft limits and transition in the interacting boson model IBM-3 are analyzed. Analytic expressions and exact eigenenergies, electromagnetic transitions probabilities are obtained for the transition between spherical and γ-soft shapes by using the Bethe ansatz within an infinite-dimensional Lie algebra in light mass nuclei. The corresponding algebraic structure and reduction chain are studied in IBM-3. For examples, the nuclear structure of the 68-76Ge and 62-70Zn isotopes is calculated in IBM-3 and compared with experimental results.

Major- and minor-metal composition of three distinct solid material fractions associated with Juan de Fuca hydrothermal fluids (northeast Pacific), and calculation of dilution fluid samples

USGS Publications Warehouse

Hinkley, T.K.; Seeley, J.L.; Tatsumoto, M.

1988-01-01

Three distinct types of solid material are associated with each sample of the hydrothermal fluid that was collected from the vents of the Southern Juan de Fuca Ridge. The solid materials appear to be representative of deposits on ocean floors near mid-ocean ridges, and interpretation of the chemistry of the hydrothermal solutions requires understanding of them. Sr isotopic evidence indicates that at least two and probably all three of these solid materials were removed from the solution with which they are associated, by precipitation or adsorption. This occurred after the "pure" hydrothermal fluid was diluted and thoroughly mixed with ambient seawater. The three types of solid materials, are, respectively, a coarse Zn- and Fe-rich material with small amounts of Na and Ca; a finer material also rich in Zn and Fe, but with alkali and alkaline-earth metals; and a scum composed of Ba or Zn, with either considerable Fe or Si, and Sr. Mineral identification is uncertain because of uncertain anion composition. Only in the cases of Ba and Zn were metal masses greater in solid materials than in the associated fluids. For all other metals measured, masses in fluids dwarf those in solids. The fluids themselves contain greater concentrations of all metals measured, except Mg, than seawater. We discuss in detail the relative merits of two methods of determining the mixing proportions of "pure" hydrothermal solution and seawater in the fluids, one based on Sr isotopes, and another previously used method based on Mg concentrations. Comparison of solute concentrations in the several samples shows that degree of dilution of "pure" hydrothermal solutions by seawater, and amounts of original solutes that were removed from it as solid materials, are not related. There is no clear evidence that appreciable amounts of solid materials were not conserved (lost) either during or prior to sample collection. ?? 1988.

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.

The cycling of iron, zinc and cadmium in the North East Pacific Ocean - Insights from stable isotopes

NASA Astrophysics Data System (ADS)

Conway, Tim M.; John, Seth G.

2015-09-01

Dissolved stable isotope ratios of the transition metals provide useful information, both for understanding the cycling of these bioactive trace elements through the oceans, and tracing their marine sources and sinks. Here, we present seawater dissolved Fe, Zn and Cd concentration and stable isotope ratio (δ56Fe, δ66Zn, and δ114Cd) profiles from two stations in the Pacific Ocean, the SAFe Station (30°N 140°W) in the subtropical North East Pacific from the GEOTRACES IC2 cruise, and the marginal San Pedro Basin (33.8°N 118.4°W) within the South California Bight. These data represent, to our knowledge, the first full-water column profiles for δ66Zn and δ56Fe from the open-ocean North Pacific, and the first observations of dissolved δ66Zn and δ114Cd in a low-oxygen marginal basin. At the SAFe station, δ56Fe is isotopically lighter throughout the water column (-0.6 to +0.1‰, relative to IRRM-014) compared to the North Atlantic, suggesting significant differences in Fe sources or Fe cycling between these two ocean basins. A broad minimum in δ56Fe associated with the North Pacific oxygen minimum zone (OMZ; <75 μmol kg-1 dissolved oxygen; ∼550-2000 m depth) is consistent with reductive sediments along the California margin being an important source of dissolved Fe to the North Pacific. Other processes which may influence δ56Fe at SAFe include biological cycling in the upper ocean, and input of Fe from hydrothermal vents and oxic sediments below the OMZ. Zn and Cd concentration profiles at both stations broadly match the distribution of the macronutrients silicate and phosphate, respectively. At SAFe, δ114Cd increases towards the surface, reflecting the biological preference for assimilation of lighter Cd isotopes, while negative Cd∗ (-0.12) associated with low oxygen waters supports the recently proposed hypothesis of water-column CdS precipitation. In contrast to δ114Cd, δ66Zn at SAFe decreases towards the surface ocean, perhaps due to scavenging of isotopically heavy Zn, while at intermediate depths δ66Zn provides further evidence of a mid-depth dissolved δ66Zn maximum. We suggest this may be a global feature of Zn biogeochemistry related to either regeneration of heavy adsorbed Zn, or to ZnS formation and removal within the water column. Data from San Pedro shows that anoxic sediments can be a source of isotopically light Zn to the water column (δ66Zn of ∼-0.3‰ relative to JMC Lyon), though evidence of this signal is not observed being transported to SAFe. Within North Pacific Intermediate Water at SAFe (NPIW; ∼500 m) elevated Cd∗ and Zn∗ and a focused minimum in δ56Fe suggest possible transport of Fe, Zn, and Cd over thousands of km from subpolar waters, meaning that NPIW may have a strong influence on the subsurface distribution of trace metals throughout the North Pacific.

Predicting the solubility and lability of Zn, Cd, and Pb in soils from a minespoil-contaminated catchment by stable isotopic exchange

NASA Astrophysics Data System (ADS)

Marzouk, E. R.; Chenery, S. R.; Young, S. D.

2013-12-01

The Rookhope catchment of Weardale, England, has a diverse legacy of contaminated soils due to extensive lead mining activity over four centuries. We measured the isotopically exchangeable content of Pb, Cd and Zn (E-values) in a large representative subset of the catchment soils (n = 246) using stable isotope dilution. All three metals displayed a wide range of %E-values (c. 1-100%) but relative lability followed the sequence Cd > Pb > Zn. A refinement of the stable isotope dilution approach also enabled detection of non-reactive metal contained within suspended sub-micron (<0.22 μm) colloidal particles (SCP-metal). For most soils, the presence of non-labile SCP-metal caused only minor over-estimation of E-values (<2%) but the effect was greater for soils with particularly large humus or carbonate contents. Approximately 80%, 53% and 66% of the variability in Zn, Cd and Pb %E-values (respectively) could be explained by pH, loss on ignition and total metal content. E-values were affected by the presence of ore minerals at high metal contents leading to an inconsistent trend in the relationship between %E-value and soil metal concentration. Metal solubility, in the soil suspensions used to measure E-values, was predicted using the WHAM geochemical speciation model (versions VI and VII). The use of total and isotopically exchangeable metal as alternative input variables was compared; the latter provided significantly better predictions of solubility, especially in the case of Zn. Lead solubility was less well predicted by either version of WHAM, with over-prediction at low pH and under-prediction at high soil pH values. Quantify the isotopically exchangeable fractions of Zn, Cd and Pb (E-values), and assess their local and regional variability, using multi-element stable isotope dilution, in a diverse range of soil ecosystems within the catchment of an old Pb/Zn mining area. Assess the controlling influences of soil properties on metal lability and develop predictive algorithms for metal lability in the contaminated catchment based on simple soil properties (such as pH, organic matter (LOI), and total metal content). Examine the incidence of non-isotopically-exchangeable metal held within suspended colloidal particles (SCP-metal) in filtered soil solutions (<0.22 μm) by comparing E-values from isotopic abundance in solutions equilibrated with soil and in a resin phase equilibrated with the separated solution. Assess the ability of a geochemical speciation model, WHAM(VII), to predict metal solubility using isotopically exchangeable metal as an input variable.

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.

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.

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.

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

Fe, Zn, and Cd stable isotopes from the eastern tropical South Pacific from GEOTRACES cruise GP16 - Methods and data

NASA Astrophysics Data System (ADS)

Helgoe, J. M.; Townsend, E.; John, S.

2014-12-01

A new method has been developed for the rapid analysis of metal concentrations and stable isotope ratios using a prepFAST automated sample processing robot. Although concentrations and isotopes are processed separately, similar methods are used for both. Initially all seawater is acidified to pH 2. Then Nobias resin with EDTA/IDA functional groups is added to either 10mL of sample for concentrations or ~1L samples for isotopes. Fe binds to the resin at low pH, and the pH is subsequently raised to allow Zn and Cd to bind. For concentration analyses, all subsequent chemistry is automated on the prepFAST including removal of seawater, rinsing of resin, and elution of resin into acid. For isotope samples these extraction techniques are performed manually, but the subsequent purification of Fe, Zn, and Cd by anion exchange chromatography is automated using the prepFAST. With these new methods, samples from the US GEOTRACES cruise GP16, in the eastern tropical South Pacific, are being analyzed. High concentrations of dissolved Fe are observed near the continental shelf and near submarine hydrothermal vents. Interestingly, isotope data show that dissolved Fe near the continental shelf generally has a δ56Fe close to 0 ‰. This δ56 Fe signature is suggestive of a non-reductive dissolution source for Fe, as Fe(II) released by reductive dissolution is typically closer to -2 ‰. Preliminary data show nutrient-type profiles for Zn and Cd, with Zn matching Si and Cd having a similar distribution to P. An increase in dissolved Zn near hydrothermal vents suggests a possible hydrothermal zinc source to the deep ocean. Continuing analysis of isotope data will reveal more about the source and biogeochemical cycling of these three chemically and biologically important trace metals throughout the eastern tropical Pacific Ocean.

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.

Ion microprobe analysis of {sup 18}O/{sup 16}O in authigenic and detrital quartz in the St. Peter Sandstone, Michigan Basin and Wisconsin Arch, USA: Contrasting diagenetic histories

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

Graham, C.M.; Valley, J.W.; Winter, B.L.

1996-12-01

The oxygen isotopic compositions of authigenic quartz cements in sandstones provide a monitor of the temperatures, compositions, and origins of pore-occluding fluids during diagenesis, but quartz overgrowths are too fine-grained to be amenable to conventional isotopic analysis. We have used a Cameca ims-4f ion microprobe to determine oxygen isotopic variations in authigenic and detrital quartz in four samples of the Ordovician St. Peter Sandstone from the Michigan Basin and Wisconsin Arch, midwestern USA. Ion microprobe isotopic analyses have been successfully accomplished with an internal precision of {+-}1{per_thousand} (1{sigma}) and a spatial resolution of 20-30 {mu}m at low mass resolution usingmore » a high voltage offset technique. Repeated analyses of the quartz standard demonstrate a reproducibility of close to {+-}1{per_thousand} (1 sd) in good agreement with that expected from counting statistics. Conventional and ion microprobe analyses are mutually consistent, supporting the accuracy of the ion microprobe analyses. Within-sample isotopic variations of up to 13{per_thousand} and micro-scale isotopic variations of at least 4{per_thousand} over a distance of 100 {mu}m have been measured within quartz overgrowths in a sandstone from the Wisconsin Arch. Overgrowths are uniformly higher in {delta}{sup 18}O than detrital grains, and gradients of up to 25% exist across a few microns. {sup 18}O-enriched quartz overgrowths in sandstones from the Wisconsin Arch show complex CL zonation and reflect one of two possible processes: (1) low-temperature quartz precipitation during mixing of meteoric waters with upwelling basinal fluids; (2) higher temperature quartz precipitation during episodic gravity-driven upwelling of warm basinal fluids (of comparable isotopic composition to Michigan Basin fluids) from the Illinois Basin, related to evolution of Mississippi Valley type Pb-Zn ore-forming fluids. 59 refs., 7 figs., 4 tabs.« less

EDTA Shuttle Effect vs. Lignosulfonate Direct Effect Providing Zn to Navy Bean Plants (Phaseolus vulgaris L ‘Negro Polo’) in a Calcareous Soil

PubMed Central

Cieschi, María T.; Benedicto, Ana; Hernández-Apaolaza, Lourdes; Lucena, Juan J.

2016-01-01

Zn-Lignosulfonates (LS) fertilizers are used as an eco-friendly alternative to chelate formulations. The mechanisms of Zn release in the rhizosphere by both types of products are compared. The ability to provide Zn to Phaseolus vulgaris L of non-modified and chemically modified ZnLS and ZnEDTA is compared in a hydroponic assay. Stable isotope 67Zn was used to study Zn source (fertilizer, ZnFer, or native, ZnNat) uptake and distribution in plants in two soil pot experiments. ZnEDTA was the best treatment to provide both ZnFer and ZnNat to navy bean plants. A shuttle effect mechanism and an isotopic exchange may occur. ZnLS from eucalyptus (ZnLSE) provides more Zn to the plant than LS from spruce. Chemical modifications of ZnLSE does not improve its efficiency. A double dose of ZnLSE provides similar ZnFer in leaves and similar soluble ZnFer content in soil than ZnEDTA. A model for the Zn fertilizers behavior in the soil and plant system is presented, showing the shuttle effect for the synthetic chelate and the direct delivery in the rhizosphere for the ZnLS complex. PMID:28018367

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.

Nature and origin of the nonsulfide zinc deposits in the Sierra Mojada District, Coahuila, Mexico: constraints from regional geology, petrography, and isotope analyses

NASA Astrophysics Data System (ADS)

Kyle, J. Richard; Ahn, Hyein; Gilg, H. Albert

2018-02-01

The Sierra Mojada District comprises multiple types of near-surface mineral concentrations ranging from polymetallic sulfide zones, "nonsulfide Zn" (NSZ) deposits, and a silver-rich Pb carbonate deposit hosted by lower Cretaceous carbonate strata. Hypogene concentrations of Fe-Zn-Pb-Cu-Ag sulfides and sulfosalts are locally preserved and are associated with hydrothermal dolomite and silica. Alteration mineralogy and sulfur isotope data suggest primary Zn-Pb-Ag mineralization from circa 200 °C hydrothermal fluids. The NSZ deposits dominantly consist of smithsonite and hemimorphite associated with local Mn-Fe oxides. The Red Zinc Zone consists of strata-bound zones dominantly of hemimorphite that fills pores in residual and resedimented Fe oxides. The White Zinc Zone shows local dissolution features, including internal sediments interbanded with and cemented by smithsonite. Similar Pb isotopic compositions of smithsonite, hemimorphite, and cerussite to Sierra Mojada galena document that the NSZ deposits originated from polymetallic carbonate-replacement sulfide deposits, with flow of metal-bearing groundwater being controlled by local topography and structural features in this extensional terrane. Oxygen isotope values for Sierra Mojada smithsonite are relatively constant (δ18OVSMOW = 20.9 to 23.3‰) but are unusually low compared to other supergene smithsonites. Using δ18OVSMOW (- 8‰) of modern groundwater at nearby Cuatrociénegas, smithsonite formational temperatures are calculated to have been between 26 to 35 °C. Smithsonite precipitation was favored by near-neutral conditions typical of carbonate terranes, whereas hemimorphite precipitated by reaction with wallrock silica and locally, or episodically, more acidic conditions resulting from sulfide oxidation. Transition to, and stabilization of, the modern desert climate over the past 9000 years from the Late Pleistocene wetter, cooler climate of northern Mexico resulted in episodic drawdown of the water table and termination of local supergene metal mobilization.

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.

METHOD FOR PURIFYING URANIUM

DOEpatents

Kennedy, J.W.; Segre, E.G.

1958-08-26

A method is presented for obtaining a compound of uranium in an extremely pure state and in such a condition that it can be used in determinations of the isotopic composition of uranium. Uranium deposited in calutron receivers is removed therefrom by washing with cold nitric acid and the resulting solution, coataining uranium and trace amounts of various impurities, such as Fe, Ag, Zn, Pb, and Ni, is then subjected to various analytical manipulations to obtain an impurity-free uranium containing solution. This solution is then evaporated on a platinum disk and the residue is ignited converting it to U2/sub 3//sub 8/. The platinum disk having such a thin film of pure U/sub 2/O/sub 8/ is suitable for use with isotopic determination techaiques.

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.

Phosphorite-hosted zinc and lead mineralization in the Sekarna deposit (Central Tunisia)

NASA Astrophysics Data System (ADS)

Garnit, Hechmi; Bouhlel, Salah; Barca, Donatella; Johnson, Craig A.; Chtara, Chaker

2012-06-01

The Sekarna Zn-Pb deposit is located in Central Tunisia at the northeastern edge of the Cenozoic Rohia graben. Mineralization comprises two major ore types: (1) disseminated Zn-Pb sulfides that occur as lenses in sedimentary phosphorite layers and (2) cavity-filling zinc oxides (calamine-type ores) that crosscut Late Cretaceous and Early Eocene limestone. We studied Zn sulfide mineralization in the Saint Pierre ore body, which is hosted in a 5-m-thick sedimentary phosphorite unit of Early Eocene age. The sulfide mineralization occurs as replacements of carbonate cement in phosphorite. The ores comprise stratiform lenses rich in sphalerite with minor galena, Fe sulfides, and earlier diagenetic barite. Laser ablation-inductively coupled plasma mass spectrometry analyses of sphalerite and galena show a wide range of minor element contents with significant enrichment of cadmium in both sphalerite (6,000-20,000 ppm) and galena (12-189 ppm). The minor element enrichments likely reflect the influence of the immediate organic-rich host rocks. Fluid inclusions in sphalerite give homogenization temperatures of 80-130°C. The final ice melting temperatures range from -22°C to -11°C, which correspond to salinities of 15-24 wt.% NaCl eq. and suggest a basinal brine origin for the fluids. Sulfur isotope analyses show uniformly negative values for sphalerite (-11.2‰ to -9.3‰) and galena (-16‰ to -12.3‰). The δ34S of barite, which averages 25.1‰, is 4‰ higher than the value for Eocene seawater sulfate. The sulfur isotopic compositions are inferred to reflect sulfur derivation through bacterial reduction of contemporaneous seawater sulfate, possibly in restricted basins where organic matter was abundant. The Pb isotopes suggest an upper crustal lead source.

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.

Mineralogical, textural, sulfur and lead isotope constraints on the origin of Ag-Pb-Zn mineralization at Bianjiadayuan, Inner Mongolia, NE China

NASA Astrophysics Data System (ADS)

Zhai, Degao; Liu, Jiajun; Cook, Nigel J.; Wang, Xilong; Yang, Yongqiang; Zhang, Anli; Jiao, Yingchun

2018-04-01

The Bianjiadayuan Ag-Pb-Zn deposit (4.81 Mt. @157.4 g/t Ag and 3.94% Pb + Zn) is located in the Great Hinggan Range Pb-Zn-Ag-Cu-Mo-Sn-Fe polymetallic metallogenic belt, NE China. Vein type Pb-Zn-Ag ore bodies are primarily hosted by slate, adjacent to a Sn ± Cu ± Mo mineralized porphyry intrusion. The deposit is characterized by silver-rich ores with Ag grades up to 3000 g/t. Four primary paragenetic sequences are recognized: (I) arsenopyrite + pyrite + quartz, (II) main sulfide + quartz, (III) silver-bearing sulfosalt + quartz, and (IV) boulangerite + calcite. A subsequent supergene oxidation stage has also been identified. Hydrothermal alteration consists of an early episode of silicification, two intermediate episodes (propylitic and phyllic), and a late argillic episode. Silver mineralization primarily belongs to the late paragenetic sequence III. Freibergite is the dominant and most important Ag-mineral in the deposit. Detailed ore mineralogy of Bianjiadayuan freibergite reveals evidence of chemical heterogeneity down to the microscale. Silver-rich sulfosalts in the late paragenetic sequence III are largely derived from a series of retrograde and solid-state reactions that redistribute Ag via decomposition and exsolution during cooling, illustrating that documentation of post-mineralization processes is essential for understanding silver ore formation. Sulfur and lead isotope compositions of sulfides, and comparison with those of local various geological units, indicate that the ore-forming fluids, lead, and other metals have a magmatic origin, suggesting a close genetic association between the studied Ag-Pb-Zn veins and the local granitic intrusion. Fluid cooling coupled with decreases in fO2 and fS2 are the factors inferred to have led to a decrease of silver solubility in the hydrothermal fluid, and successively promoted extensive Ag deposition.

Coulomb Excitation of the N = 50 nucleus 80Zn

NASA Astrophysics Data System (ADS)

van de Walle, J.; Aksouh, F.; Ames, F.; Behrens, T.; Bildstein, V.; Blazhev, A.; Cederkäll, J.; Clément, E.; Cocolios, T. E.; Davinson, T.; Delahaye, P.; Eberth, J.; Ekström, A.; Fedorov, D. V.; Fedosseev, V. N.; Fraile, L. M.; Franchoo, S.; Gernhauser, R.; Georgiev, G.; Habs, D.; Heyde, K.; Huber, G.; Huyse, M.; Ibrahim, F.; Ivanov, O.; Iwanicki, J.; Jolie, J.; Kester, O.; Köster, U.; Kröll, T.; Krücken, R.; Lauer, M.; Lisetskiy, A. F.; Lutter, R.; Marsh, B. A.; Mayet, P.; Niedermaier, O.; Nilsson, T.; Pantea, M.; Perru, O.; Raabe, R.; Reiter, P.; Sawicka, M.; Scheit, H.; Schrieder, G.; Schwalm, D.; Seliverstov, M. D.; Sieber, T.; Sletten, G.; Smirnova, N.; Stanoiu, M.; Stefanescu, I.; Thomas, J.-C.; Valiente-Dobón, J. J.; van Duppen, P.; Verney, D.; Voulot, D.; Warr, N.; Weisshaar, D.; Wenander, F.; Wolf, B. H.; Zielińska, M.

2008-05-01

Neutron rich Zinc isotopes, including the N = 50 nucleus 80Zn, were produced and post-accelerated at the Radioactive Ion Beam (RIB) facility REX-ISOLDE (CERN). Low-energy Coulomb excitation was induced on these isotopes after post-acceleration, yielding B(E2) strengths to the first excited 2+ states. For the first time, an excited state in 80Zn was observed and the 21+ state in 78Zn was established. The measured B(E2,21+-->01+) values are compared to two sets of large scale shell model calculations. Both calculations reproduce the observed B(E2) systematics for the full Zinc isotopic chain. The results for N = 50 isotones indicate a good N = 50 shell closure and a strong Z = 28 proton core polarization. The new results serve as benchmarks to establish theoretical models, predicting the nuclear properties of the doubly magic nucleus 78Ni.

Source Identification of Zn Contamination around a Zn-smelting Facility in Korea

NASA Astrophysics Data System (ADS)

Lee, S.; Jeon, S. K.

2016-12-01

With massive production of Zn for various industrial purposes, Zn release into the environment becomes highly possible, some of which might require a proper countermeasure depending on the residual concentration in environmental media. In order to set up an effective countermeasure, identification of contaminant source should be essential for determining the target object to be managed, and delineating the extent of necessary remedial work. In this study, we focus on a Zn-smelting facility located in eastern Korea where Zn concentrations in surrounding soils have been reported to exceed the contamination criteria. An abandoned mine which had been explored for Zn ores was located adjacent to the facility, and background concentration of Zn in the area was naturally high. The objective of the present study is to identify the major source of Zn contamination in the area, and to estimate the relative contributions of multiple sources, if so. In order to achieve these goals, we analyzed and compared the stable isotope ratios of Pb in the soil samples collected at different distances from the facility and the Zn concentrates (ZnS, sphalerite) of raw material in the facility. The Pb isotope ratios were further investigated by performing sequential extraction for each sample and comparing the isotopes ratios observed in each fraction of soil. In addition, possible presence of ZnS in the samples, which could be an evidence of Zn contamination by the smelting facility, was estimated by X-ray diffraction (XRD) analysis and scanning electron microscopy equipped with energy dispersive X-ray spectrometry (SEM-EDS) after separating the soil sample into the fractions with different particle sizes

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.

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.

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.

An enriched stable-isotope approach to determine the gill-zinc binding properties of juvenile rainbow trout (Oncorhynchus mykiss) during acute zinc exposures in hard and soft waters

USGS Publications Warehouse

Todd, A.S.; Brinkman, S.; Wolf, R.E.; Lamothe, P.J.; Smith, K.S.; Ranville, J.F.

2009-01-01

The objective of the present study was to employ an enriched stable-isotope approach to characterize Zn uptake in the gills of rainbow trout (Oncorhynchus mykiss) during acute Zn exposures in hard water (???140 mg/L as CaCO 3) and soft water (???30 mg/L as CaCO3). Juvenile rainbow trout were acclimated to the test hardnesses and then exposed for up to 72 h in static exposures to a range of Zn concentrations in hard water (0-1,000 ??g/L) and soft water (0-250 ??g/L). To facilitate detection of new gill Zn from endogenous gill Zn, the exposure media was significantly enriched with 67Zn stable isotope (89.60% vs 4.1% natural abundance). Additionally, acute Zn toxicity thresholds (96-h median lethal concentration [LC50]) were determined experimentally through traditional, flow-through toxicity tests in hard water (580 ??g/L) and soft water (110 ??g/L). Following short-term (???3 h) exposures, significant differences in gill accumulation of Zn between hard and soft water treatments were observed at the three common concentrations (75, 150, and 250 ??g/L), with soft water gills accumulating more Zn than hard water gills. Short-term gill Zn accumulation at hard and soft water LC50s (45-min median lethal accumulation) was similar (0.27 and 0.20 ??g/g wet wt, respectively). Finally, comparison of experimental gill Zn accumulation, with accumulation predicted by the biotic ligand model, demonstrated that model output reflected short-term (<1 h) experimental gill Zn accumulation and predicted observed differences in accumulation between hard and soft water rainbow trout gills. Our results indicate that measurable differences exist in short-term gill Zn accumulation following acclimation and exposure in different water hardnesses and that short-term Zn accumulation appears to be predictive of Zn acute toxicity thresholds (96-h LC50s). ?? 2009 SETAC.

Mercury isotope constraints on the source for sediment-hosted lead-zinc deposits in the Changdu area, southwestern China

NASA Astrophysics Data System (ADS)

Xu, Chunxia; Yin, Runsheng; Peng, Jiantang; Hurley, James P.; Lepak, Ryan F.; Gao, Jianfeng; Feng, Xinbin; Hu, Ruizhong; Bi, Xianwu

2018-03-01

The Lanuoma and Cuona sediment-hosted Pb-Zn deposits hosted by Upper Triassic limestone and sandstone, respectively, are located in the Changdu area, SW China. Mercury concentrations and Hg isotopic compositions from sulfide minerals and potential source rocks (e.g., the host sedimentary rocks and the metamorphic basement) were investigated to constrain metal sources and mineralization processes. In both deposits, sulfide minerals have higher mercury (Hg) concentrations (0.35 to 1185 ppm) than the metamorphic basement rocks (0.05 to 0.15 ppm) and sedimentary rocks (0.02 to 0.08 ppm). Large variations of mass-dependent fractionation (3.3‰ in δ202Hg) and mass-independent fractionation (0.3‰ in Δ199Hg) of Hg isotopes were observed. Sulfide minerals have Hg isotope signatures that are similar to the hydrothermal altered rocks around the deposit, and similar to the metamorphic basement, but different from barren sedimentary rocks. The variation of Δ199Hg suggests that Hg in sulfides was mainly derived from the underlying metamorphic basement. Mercury isotopes could be a geochemical tracer in understanding metal sources in hydrothermal ore deposits.

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.

Dual-isotope method for determination of human zinc absorption: the use of a test meal of turkey meat

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

Flanagan, P.R.; Cluett, J.; Chamberlain, M.J.

The percentage of /sup 65/Zn taken up (absorbed) from extrinsically labeled turkey meat was calculated from the amounts of /sup 65/Zn and a nonabsorbed /sup 51/Cr marker present in the body or in a single stool specimen after 1-2 d. /sup 51/CrCl/sub 3/ proved to be a suitable marker for unabsorbed /sup 65/Zn and so the early determination of /sup 65/Zn absorption was possible. With stool counting, /sup 65/Zn absorption data from first stool samples after 1-2 d were accurate as judged by correlation with the amount of /sup 65/Zn in the body 7-10 d later (retention); results from subsequentmore » stools gave lower absorption values due to the early excretion of some absorbed /sup 65/Zn. The dual-isotope method gave reproducible results when four successive tests of zinc absorption were carried out in a group of six subjects. The average (mean +/- SD) /sup 65/Zn absorption from turkey meals containing 31 mumol (2 mg) and 46 mumol (3 mg) of zinc was 39 +/- 8% and 29 +/- 6%, respectively, measured by stool counting; /sup 65/Zn absorption and retention correlated well in both studies. A series of different beverages was given in place of water with the turkey meal. Orange juice significantly reduced /sup 65/Zn absorption and milk also showed this tendency, but tea, whiskey, wine or beer had no significant effect on the absorption of /sup 65/Zn from the turkey meal. In groups of subjects the mean ratio of /sup 65/Zn absorption from extrinsically labeled turkey meat on two occasions (1.06) was not significantly different from that of the absorption of extrinsic to intrinsic /sup 65/Zn labels (1.16). The dual-isotope technique with either stool or body counting is suitable for the rapid determination of /sup 65/Zn absorption from extrinsically labeled turkey within 2 d.« less

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.

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.

Measurement of total Zn and Zn isotope ratios by quadrupole ICP-MS for evaluation of Zn uptake in gills of brown trout (Salmo trutta) and rainbow trout (Oncorhynchus mykiss)

USGS Publications Warehouse

Wolf, R.E.; Todd, A.S.; Brinkman, S.; Lamothe, P.J.; Smith, K.S.; Ranville, J.F.

2009-01-01

This study evaluates the potential use of stable zinc isotopes in toxicity studies measuring zinc uptake by the gills of brown trout (Salmo trutta) and rainbow trout (Oncorhynchus mykiss). The use of stable isotopes in such studies has several advantages over the use of radioisotopes, including cost, ease of handling, elimination of permit requirements, and waste disposal. A pilot study using brown trout was performed to evaluate sample preparation methods and the ability of a quadrupole inductively coupled plasma mass spectrometer (ICP-MS) system to successfully measure changes in the 67Zn/66Zn ratios for planned exposure levels and duration. After completion of the pilot study, a full-scale zinc exposure study using rainbow trout was performed. The results of these studies indicate that there are several factors that affect the precision of the measured 67Zn/66Zn ratios in the sample digests, including variations in sample size, endogenous zinc levels, and zinc uptake rates by individual fish. However, since these factors were incorporated in the calculation of the total zinc accumulated by the gills during the exposures, the data obtained were adequate for their intended use in calculating zinc binding and evaluating the influences of differences in water quality parameters.

Zinc stable isotope fractionation upon accelerated oxidative weathering of sulfidic mine waste.

PubMed

Matthies, R; Krahé, L; Blowes, D W

2014-07-15

Accelerated oxidative weathering in a reaction cell (ASTM D 5744 standard protocol) was performed over a 33 week period on well characterized, sulfidic mine waste from the Kidd Creek Cu-Zn volcanogenic massive sulfide deposit, Canada. The cell leachate was monitored for physicochemical parameters, ion concentrations and stable isotope ratios of zinc. Filtered zinc concentrations (<0.45 μm) in the leachate ranged between 4.5 mg L(-1) and 1.9 g L(-1)-potentially controlled by pH, mineral solubility kinetics and (de)sorption processes. The zinc stable isotope ratios varied mass-dependently within +0.1 and +0.52‰ relative to IRMM 3702, and were strongly dependent on the pH (rpH-d66Zn=0.65, p<0.005, n=31). At a pH below 5, zinc mobilization was governed by sphalerite oxidation and hydroxide dissolution-pointing to the isotope signature of sphalerite (+0.1 to +0.16‰). Desorption processes resulted in enrichment of (66)Zn in the leachate reaching a maximum offset of +0.32‰ compared to the proposed sphalerite isotope signature. Over a period characterized by pH=6.1 ± 0.6, isotope ratios were significantly more enriched in (66)Zn with an offset of ≈ 0.23‰ compared to sphalerite, suggesting that zinc release may have been derived from a second zinc source, such as carbonate minerals, which compose 8 wt.% of the tailings. This preliminary study confirms the benefit of applying zinc isotopes alongside standard monitoring parameters to track principal zinc sources and weathering processes in complex multi-phase matrices. Copyright © 2014 Elsevier B.V. All rights reserved.

Coulomb Excitation of Neutron-Rich Zn Isotopes: First Observation of the 21+ State in Zn80

NASA Astrophysics Data System (ADS)

van de Walle, J.; Aksouh, F.; Ames, F.; Behrens, T.; Bildstein, V.; Blazhev, A.; Cederkäll, J.; Clément, E.; Cocolios, T. E.; Davinson, T.; Delahaye, P.; Eberth, J.; Ekström, A.; Fedorov, D. V.; Fedosseev, V. N.; Fraile, L. M.; Franchoo, S.; Gernhauser, R.; Georgiev, G.; Habs, D.; Heyde, K.; Huber, G.; Huyse, M.; Ibrahim, F.; Ivanov, O.; Iwanicki, J.; Jolie, J.; Kester, O.; Köster, U.; Kröll, T.; Krücken, R.; Lauer, M.; Lisetskiy, A. F.; Lutter, R.; Marsh, B. A.; Mayet, P.; Niedermaier, O.; Nilsson, T.; Pantea, M.; Perru, O.; Raabe, R.; Reiter, P.; Sawicka, M.; Scheit, H.; Schrieder, G.; Schwalm, D.; Seliverstov, M. D.; Sieber, T.; Sletten, G.; Smirnova, N.; Stanoiu, M.; Stefanescu, I.; Thomas, J.-C.; Valiente-Dobón, J. J.; van Duppen, P.; Verney, D.; Voulot, D.; Warr, N.; Weisshaar, D.; Wenander, F.; Wolf, B. H.; Zielińska, M.

2007-10-01

Neutron-rich, radioactive Zn isotopes were investigated at the Radioactive Ion Beam facility REX-ISOLDE (CERN) using low-energy Coulomb excitation. The energy of the 21+ state in Zn78 could be firmly established and for the first time the 2+→01+ transition in Zn80 was observed at 1492(1) keV. B(E2,21+→01+) values were extracted for Zn74,76,78,80 and compared to large scale shell model calculations. With only two protons outside the Z=28 proton core, Zn80 is the lightest N=50 isotone for which spectroscopic information has been obtained to date. Two sets of advanced shell model calculations reproduce the observed B(E2) systematics. The results for N=50 isotones indicate a good N=50 shell closure and a strong Z=28 proton core polarization. The new results serve as benchmarks to establish theoretical models, predicting the nuclear properties of the doubly magic nucleus Ni78.

Inelastic scattering of neutron-rich Ni and Zn isotopes off a proton target

NASA Astrophysics Data System (ADS)

Cortés, M. L.; Doornenbal, P.; Dupuis, M.; Lenzi, S. M.; Nowacki, F.; Obertelli, A.; Péru, S.; Pietralla, N.; Werner, V.; Wimmer, K.; Authelet, G.; Baba, H.; Calvet, D.; Château, F.; Corsi, A.; Delbart, A.; Gheller, J.-M.; Gillibert, A.; Isobe, T.; Lapoux, V.; Louchart, C.; Matsushita, M.; Momiyama, S.; Motobayashi, T.; Niikura, M.; Otsu, H.; Péron, C.; Peyaud, A.; Pollacco, E. C.; Roussé, J.-Y.; Sakurai, H.; Santamaria, C.; Sasano, M.; Shiga, Y.; Takeuchi, S.; Taniuchi, R.; Uesaka, T.; Wang, H.; Yoneda, K.; Browne, F.; Chung, L. X.; Dombradi, Zs.; Franchoo, S.; Giacoppo, F.; Gottardo, A.; Hadynska-Klek, K.; Korkulu, Z.; Koyama, S.; Kubota, Y.; Lee, J.; Lettmann, M.; Lozeva, R.; Matsui, K.; Miyazaki, T.; Nishimura, S.; Olivier, L.; Ota, S.; Patel, Z.; Sahin, E.; Shand, C. M.; Söderström, P.-A.; Stefan, I.; Steppenbeck, D.; Sumikama, T.; Suzuki, D.; Vajta, Zs.; Wu, J.; Xu, Z.

2018-04-01

Proton inelastic scattering of Ni,7472 and Zn,8076 ions at energies around 235 MeV/nucleon was performed at the Radioactive Isotope Beam Factory and studied using γ -ray spectroscopy. Angular integrated cross sections for direct inelastic scattering to the 21+ and 41+ states were measured. The Jeukenne-Lejeune-Mahaux folding model, extended beyond 200 MeV, was used together with neutron and proton densities stemming from quasiparticle random-phase approximation (QRPA) calculations to interpret the experimental cross sections and to infer neutron to proton matrix element ratios. In addition, coupled-channels calculations with a phenomenological potential were used to determine deformation lengths. For the Ni isotopes, correlations favor neutron excitations, thus conserving the Z =28 gap. A dominance of proton excitation, on the other hand, is observed in the Zn isotopes, pointing to the conservation of the N =50 gap approaching 78Ni. These results are in agreement with QRPA and large-scale shell-model calculations.

Origin and timescale of volatile element depletion in crustal and mantle reservoirs

NASA Astrophysics Data System (ADS)

Moynier, Frederic; Day, James M. D.

2014-05-01

Volatile elements play a fundamental role in the evolution of planets. Understanding of how volatile budgets were set in planets, and how and to what extent planetary bodies became volatile-depleted during the earliest stages of Earth and Solar System formation remain poorly understood, however. It has been proposed that the depletion is due to incomplete condensation (volatile elements were not there in the first place, in which case the timing would have to be fast, <1Myr), or that planetary bodies lost volatile elements through evaporation (post-accretion volatilization). Volatilization is known to fractionate isotopes, thus comparing isotope ratios of volatile element between samples is a powerful tool for understanding the origin of volatile element abundance variations. For example, recent work has shown that lunar basalts are enriched in the heavier isotopes of Zn (~1 ‰ for 66Zn/64Zn) compared to chondrites, terrestrial and martian basalts. We will discuss these Zn isotopic data of crustal and mantle rocks, as well as other stable isotopic systems (e.g., Si) in relation with the giant impact theory of lunar origin, as well as the lunar magma ocean and expand to other parent bodies (e.g., angrites). The timescale of depletion in volatile elements of Solar System material is estimated by using radiogenic systems for which the parent and daughter elements have different volatility. Here we focus on the Rb-Sr and Mn-Cr isotopic systems and discuss the timescales and implications for the origin of volatile element depletion (solar nebula stage vs. planetary stage).

Evaluating Volatility-controlled Isotope Fractionation During Planet Formation: Kinetics versus Equilibrium

NASA Astrophysics Data System (ADS)

Young, E. D.

2017-12-01

Recent advances in our ability to measure stable isotope ratios of light, rock-forming elements, including those for Zn, K, Fe, Si, and Mg, among others, has resulted in an emerging hypothesis that collisions among rocky planetesimals, planetary embryos, and/or proto-planets caused losses of moderately volatile elements (e.g., K) and "common" or moderately refractory elements (e.g., Mg and Si). The primary evidence is in the form of heavy isotope enrichments in rock-forming elements relative to the chondrite groups that are thought to be representative of planetary precursors. Equilibrium volatility-controlled isotope fractionation for planetesimal magma oceans might have occurred for bodies larger than 0.1% of an Earth mass (½ the mass of Pluto) as these bodies had sufficient gravity to overpower the escape velocities of hot gas at 2000K. Both Jean's escape and viscous drag hydrodynamic escape can obviate the escape velocity limit but will fractionate by mass, not by volatility. Equilibrium vapor/melt fractionation is qualitatively consistent with the greater disparity in 29Si/28Si between Earth and chondrites than in 25Mg/24Mg. However, losses of large masses of vapor are required to record the fractionation in the melts. We consider that if Earth was derived from E chondrite-like materials, the bulk composition of the Earth, assuming refractory Ca was retained, requires > 60% loss of Mg. This is a lot of vapor loss for a process relying on at least intermittent equilibrium, although it comports with the isotopic lever-rule requirements. Paradoxically, the alternative of evaporative loss of rock-forming elements requires less total mass loss. For example, the calculated Mg and Si isotopic compositions of residues resulting from evaporation of chondritic melts can fit the Mg and Si isotopic compositions of Earth, Mars, and angrites with varying background pressures and with total mass losses of near 5% or less. These mass losses are closer to, and even lower than, those suggested by Ca concentrations relative to CI chondrite. Equilibrium models achieve greater Si than Mg isotope fractionation by large mass losses while evaporation models produce this effect for small mass losses. Additional constraints involving other isotope systems as well as models for vapor loss can distinguish between the two scenarios.

SIMS depth profiling of rubber-tyre cord bonding layers prepared using 64Zn depleted ZnO

NASA Astrophysics Data System (ADS)

Fulton, W. S.; Sykes, D. E.; Smith, G. C.

2006-07-01

Zinc oxide and copper/zinc sulphide layers are formed during vulcanisation and moulding of rubber to brass-coated steel tyre reinforcing cords. Previous studies have described how zinc diffuses through the rubber-brass interface to form zinc sulphide, and combines with oxygen to create zinc oxide during dezincification. The zinc is usually assumed to originate in the brass of the tyre cord, however, zinc oxide is also present in the rubber formulation. We reveal how zinc from these sources is distributed within the interfacial bonding layers, before and after heat and humidity ageing. Zinc oxide produced using 64Zn-isotope depleted zinc was mixed in the rubber formulation in place of the natural ZnO and the zinc isotope ratios within the interfacial layers were followed by secondary ion mass spectroscopy (SIMS) depth profiling. Variations in the relative ratios of the zinc isotopes during depth profiling were measured for unaged, heat-aged and humidity-aged wire samples and in each case a relatively large proportion of the zinc incorporated into the interfacial layer as zinc sulphide was shown to have originated from ZnO in the rubber compound.

Nanofibrillated Cellulose-Assisted Synthesis of Fiber-Like ZnO-ZnFe2O4 Composites with Enhanced Visible-Light-Driven Photocatalytic Activity

NASA Astrophysics Data System (ADS)

Cai, Aijun; Guo, Aiying; Du, Liqiang; Chang, Yongfang; Wang, Xiuping

2018-05-01

In this article, fiber-like ZnO-ZnFe2O4 composites are obtained by using nanofibrillated cellulose as a biotemplate. The as-prepared composites exhibit strong absorbance in the visible-light region. The ZnO-ZnFe2O4 composites exhibit a similar bandgap (1.88 eV) compared with the ZnFe2O4 (1.85 eV). The ZnO-ZnFe2O4 composites can be easily collected by an external magnet, which contributes to improving the utilization efficiency of the photocatalysts. The photocatalytic activity of the ZnO-ZnFe2O4 catalysts was evaluated by photodegrading rhodamine B (RhB) under visible-light irradiation. Compared with ZnO and ZnFe2O4, the ZnO-ZnFe2O4 catalysts show higher photocatalytic activity due to the efficient electron-hole separation.

Tracing Waste Water with Li isotopes

NASA Astrophysics Data System (ADS)

Millot, R.; Desaulty, A. M.

2015-12-01

The contribution of human activities such as industries, agriculture and various domestic inputs, becomes more and more significant in the chemical composition of the dissolved load of rivers. Human factors act as a supplementary key process. Therefore the mass-balance for the budget of catchments and river basins include anthropogenic disturbances. In the present study, we investigate waste water tracing by the use of Li isotopes in a small river basin near Orléans in France (l'Egoutier, 15 km² and 5 km long). It is well known that Li has strategic importance for numerous industrial applications including its use in the production of batteries for both mobile devices (computers, tablets, smartphones, etc.) and electric vehicles, but also in pharmaceutical formulations. In the present work, we collected river waters samples before and after the release from a waste water treatment plant connected to an hospital. Lithium isotopic compositions are rather homogeneous in river waters with δ7Li values around -0.5‰ ± 1 along the main course of the stream (n=7). The waste water sample is very different from the natural background of the river basin with Li concentration being twice of the values without pollution and significant heavy lithium contribution (δ7Li = +4‰). These preliminary results will be discussed in relation with factors controlling the distribution of Li and its isotopes in this specific system and compared with the release of other metals such as Pb or Zn.

Incorporation of ZnO and their composite nanostructured material into a cotton fabric platform for wearable device applications.

PubMed

Veluswamy, Pandiyarasan; Sathiyamoorthy, Suhasini; Khan, Faizan; Ghosh, Aranya; Abhijit, Majumdar; Hayakawa, Yasuhiro; Ikeda, Hiroya

2017-02-10

The central idea of this paper is to innovate a new approach for the development of wearable device materials through the coating of cotton fabric with ZnO and Sb-/Ag-/ZnO composites. The study was designed in order to have a clear understanding of the role of ZnO as well as the modified composite thereof under investigation. Cotton fabric with uniform ZnO/ZnO-composite layers on the surface was successfully synthesized via a solvothermal method. The growth behaviors were investigated by comparing ZnO and ZnO-composites. The structural, morphological, chemical states, optical, electrical and thermopower properties of these fabrics were studied. Nanostructured ZnO-composite fabric had enhanced UV shielding with a value of 83.96. It is found that the ZnO-composite fabrics have increased electrical conductivity. The thermopower value of the ZnO-composite fabric could reach 471.9μVK -1 . Such materials are anticipated to be worthwhile as wearable electronic devices and as protective textiles. Copyright © 2016 Elsevier Ltd. All rights reserved.

Late-Hercynian intrusion-related gold deposits: An integrated model on the Tighza polymetallic district, central Morocco

NASA Astrophysics Data System (ADS)

Éric, Marcoux; Khadija, Nerci; Yannick, Branquet; Claire, Ramboz; Gilles, Ruffet; Jean-Jacques, Peucat; Ross, Stevenson; Michel, Jébrak

2015-07-01

Gold have been recently recognized in the Tighza (formerly Jebel Aouam) district, in the Hercynian belt of central Morocco. This district has long been known for its W mineralization, as well as major Pb-Ag-Zn, and minor Sb-Ba deposits, all geographically associated with late-Hercynian calc-alkaline magmatism. Gold mineralization in the district is mainly hosted by thick W-Au quartz veins located around the "Mine granite" small granitic plug. Within the veins, gold grade is highest (up to 70 g/t) close to the granite but rapidly decreases going outward from the granite, defining a perigranitic zoning. Anomalous gold grades have also been measured in hydrothermal skarn layers close to two other granitic plugs (Kaolin granite and Mispickel granite), associated with disseminated As-Fe sulfides. The paragenetic sequence for the W-Au quartz veins shows three stages: (1) an early oxidized stage with wolframite-scheelite associated with early quartz (Q1), (2) an intermediate Bi-As-Te-Mo-Au sulfide stage with loellingite, bismuth minerals and native gold with a later quartz (Q2), restricted to a narrow distance from the granite, and (3) a late lower temperature As-Cu-Zn-(Pb) stage with abundant massive pyrrhotite, arsenopyrite and sphalerite, locally forming independent veins ("pyrrhotite vein"). Both Q1 hyaline and Q2 saccharoidal gold-bearing quartz display aqua-carbonic fluids with minor H2S and Cu and an homogeneous composition (81 mole% H2O, 18 mole% CO2 and about 1 mole% NaCl). The trapping pressure is estimated to 1.5-2 kbar with temperature ranging from 300 to 350 °C. Q1 inclusions have exploded indicating an uplift of the Tighza block, that lead to saccharoidal Q2 quartz deposition with multiphase NaCl-saturated fluid inclusions. 40Ar/39Ar dating demonstrates that the "Mine granite", tungsten skarnoid, scheelite-molybdenite veins, and very likely gold-bearing veins are coeval, emplaced at 286 ± 1 Ma. Multiple and widespread metal sources are indicated by radiogenic isotope studies. Nd and Sr isotope compositions of scheelite and granites suggest the participation of a juvenile component while lead isotopes demonstrate a major participation of the basement. Both gold mineralization and zoning suggest that the system developed at the end of the magmatic activity, accompanying a major transition in magmatic fluid composition. The morphology of the gold-bearing mineralization is dependent of the permeability and the reactivity of host-rocks: focus circulation of fluids through pre-existing tectonic corridors, reactivated by late-Hercynian intrusions favor the formation of large W-type gold veins, while infiltration of fluid within reactive stratigraphic layers gives rise to skarn mineralization. A 40Ar/39Ar date (W1 north vein: 291.8 ± 0.3 Ma) indicates that hydrothermal circulation predates gold and tungsten deposition in open fractures as well as Mine granite emplacement. The W-Au mineralization preceded the onset of a large convective hydrothermal cell around the intrusion that led to the formation of the Pb-Ag-Zn mined veins. The Tighza polymetallic district displays numerous similarities with the R-IRG model that was defined in the American Cordillera, such as thermal and zonation patterns, carbonic hydrothermal fluids and chronology of intrusion and related deposits, but also provides new insight to the R-IRG model such as wide Au-quartz veins instead of sheeted Au-veins, oxidation state of the magma, and Sr-Nd isotopic data. These results establish a major magmatic contribution and discard a direct genetic relationship between gold mineralization and major neighboring Pb-Ag-Zn veins. A large number of classic Pb-Zn district of the Western Hercynides belong to the same clan.

Size effect of ZnO nanorods on physicochemical properties of plasticized starch composites.

PubMed

Guz, L; Famá, L; Candal, R; Goyanes, S

2017-02-10

This work demonstrates that the size of ZnO nanorods (ZnONR) with similar aspect ratio determines several physicochemical and microbiological properties of thermoplastic starch composites (TPS/ZnONR) at a given concentration of ZnONRs. A combination of sol-gel and hydrothermal methods was developed to synthesize ZnONR with different sizes but similar aspect ratios. Starch composites containing 1wt.% of ZnONR were prepared by casting. Composites with smaller size nanorods (ZnONR-S) showed more efficiency in shielding UVA radiation and had a higher solubility and water vapor permeability than those with larger nanorods (ZnONR-L). Mechanical properties, biodegradability and antibacterial activity were also influenced by the size of the ZnONR. X-ray diffraction analysis showed that composites with ZnONR-S maintained the typical B-V type starch structure, intensifying the V-type starch structure peaks, while composite with ZnONR-L induced the formation of an amorphous structure, preventing starch retrogradation during storage. Properties affected by nanorods size are fundamental in determining composite applications. Copyright © 2016 Elsevier Ltd. All rights reserved.

A Zn-porphyrin complex contributes to bright red color in Parma ham.

PubMed

Wakamatsu, J; Nishimura, T; Hattori, A

2004-05-01

The Italian traditional dry-cured ham (Parma ham) shows a stable bright red color that is achieved without the use of nitrite and/or nitrate. In this study we examined the pigment spectroscopically, fluoroscopically and by using HPLC and ESI-HR-MASS analysis. Porphyrin derivative other than acid hematin were contained in the HCl-containing acetone extract from Parma ham. A strong fluorescence peak at 588 nm and a weak fluorescence peak at 641 nm were observed. By HPLC analysis the acetone extract of Parma ham was observed at the single peak, which eluted at the same time as Zn-protoporphyrin IX and emitted fluorescence. The results of ESI-HR-MS analysis showed both agreement with the molecular weight of Zn-protoporphyrin IX and the characteristic isotope pattern caused by Zn isotopes. These results suggest that the bright red color in Parma ham is caused by Zn-protoporphyrin IX.

Nonstoichiometric Zn Ferrite and ZnFe2O4/Fe2O3 Composite Spheres: Preparation, Magnetic Properties, and Chromium Removal

NASA Astrophysics Data System (ADS)

Hang, Chun-Liang; Yang, Li-Xia; Sun, Chang-Mei; Liang, Ying

2018-03-01

Monodisperse and porous nonstoichiometric Zn ferrite can be prepared by a solvothermal method. Such non-Zn ferrite was used to be the precursor for synthesis of ZnFe2O4/Fe2O3 composite via calcination at 600°C for 3 h in air. X-ray powder diffractometer (XRD) and Energy Dispersive Spectrometer (EDS) proved the nonstoichiometry of Zn ferrite synthesized by solvothermal method and the formation of ZnFe2O4/Fe2O3 composite via calcination. TEM image showed that non-Zn ferrite spheres with wormlike nanopore structure were made of primary nanocrystals. BET surface area of non-Zn ferrite was much higher than that of ZnFe2O4/Fe2O3 composite. Saturation magnetization of non-Zn ferrites was significantly higher than that of ZnFe2O4/Fe2O3 composites. Calcination of non-Zn ferrite resulted in the formation of large amount of non-magnetic Fe2O3,which caused a low magnetization of composite. Because of higher BET surface area and higher saturation magnetization, non-Zn ferrite presented better Cr6+ adsorption property than ZnFe2O4/Fe2O3 composites.

Zinc isotope ratio imaging of rat brain thin sections from stable isotope tracer studies by LA-MC-ICP-MS.

PubMed

Urgast, Dagmar S; Hill, Sarah; Kwun, In-Sook; Beattie, John H; Goenaga-Infante, Heidi; Feldmann, Jörg

2012-10-01

Zinc stable isotope tracers (⁶⁷Zn and ⁷⁰Zn) were injected into rats at two different time points to investigate the feasibility of using tracers to study zinc kinetics at the microscale within distinct tissue features. Laser ablation coupled to multi-collector ICP-MS was used to analyse average isotope ratios in liver thin sections and to generate bio-images showing zinc isotope ratio distribution in brain thin sections. Average isotope ratios of all samples from treated animals were found to be statistically different (P < 0.05) from samples from untreated control animals. Furthermore, differing isotope ratios in physiological features of the brain, namely hippocampus, amygdala, cortex and hypothalamus, were identified. This indicates that these regions differ in their zinc metabolism kinetics. While cortex and hypothalamus contain more tracer two days after injection than 14 days after injection, the opposite is true for hippocampus and amygdala. This study showed that stable isotope tracer experiments can be combined with laser ablation MC-ICP-MS to measure trace element kinetics in tissues at a microscale level.

Isotopic composition of Pb in ore deposits of the Betic Cordillera, Spain; origin and relationship to other European deposits

USGS Publications Warehouse

Arribas , Antonio; Tosdal, Richard M.

1994-01-01

The Betic Cordillera in southern Spain is a complex Alpine fold belt that resulted from the Cretaceous through Cenozoic collision of Africa with Europe. The region is illustrative of one of the characteristics of the Alpine-Mediterranean orogen: the occurrence over a limited area of mineral deposits with a wide variety of host rocks, mineralization ages, and styles. The metamorphic basement in the Betic zone is characterized by a nappe structure of superimposed tectonostratigraphic units and consists of lower Paleozoic to Lower Triassic clastic metasedimentary rocks. This is overlain by Middle to Upper Triassic platform carbonate rocks with abundant strata-bound F-Pb-Zn-(Ba) deposits (e.g., Sierra de Gador, Sierra Alhamilla). Cretaceous to Paleogene subduction-related compression in southeastern Spain was followed by Miocene postcollisional extension and resulted in the formation of the Almeria-Cartagena volcanic belt and widespread hydrothermal activity and associated polymetallic mineralization. Typical Miocene hydrothermal deposits include volcanic-hosted Au (e.g., Rodalquilar) and Ag-rich base metal (e.g., Cabo de Gata, Mazarron) deposits as well as complex polymetallic veins, mantos, and irregular replacement bodies which are hosted by Paleozoic and Mesozoic metamorphic rocks and Neogene sedimentary and volcanic rocks (e.g., Cartagena, Sierra Almagrera, Sierra del Aguilon, Loma de Bas).Lead isotope compositions were measured on sulfide samples from nine ore districts and from representative fresh samples of volcanic and basement rock types of the region. The results have been used to evaluate ore-forming processes in southeastern Spain with emphasis on the sources of metals. During a Late Triassic mineralizing event, Pb was leached from Paleozoic clastic metasedimentary rocks and incorporated in galena in strata-bound F-Pb-Zn-(Ba) deposits ( 206 Pb/ 204 Pb = 18.332 + or - 12, 207Pb/ 204 Pb = 15.672 + or - 12, 208 Pb/ 204 Pb = 38.523 + or - 46). The second episode of mineralization was essentially contemporaneous (late Miocene) throughout the region and did not involve remobilization of less radiogenic Triassic ore Pb. Lead isotope data indicate a dominantly Paleozoic metasedimentary source for polymetallic vein- and manto-type deposits that formed by hydrothermal circulation through the Betic basement, driven by Miocene intrusions ( 206 Pb/ 204 Pb = 18.747 + or - 20, 207 Pb/ 204Pb = 15.685 + or - 9, 208 /Pb/ 204 Pb = 39.026 + or - 37). Lead in Au-(Cu-Te-Sn) ores is isotopically indistinguishable from that of the calc-alkalic volcanic host ( 206 Pb/ 204 Pb = 18.860 + or - 9, 207 Pb/ 204 Pb = 15.686 + or - 8, 208 Pb/ 204 Pb = 38.940 + or - 27). In contrast, the Pb in volcanic-hosted Pb-Zn-Cu-(Ag-Au) veins was derived from Paleozoic metamorphic and Miocene volcanic rocks ( 206 Pb/ 204 Pb = 18.786 + or - 5, 207 Pb/ 204 Pb = 15.686 + or - 2, 208 Pb/ 204 Pb = 38.967 + or - 9).A comparison of the Pb isotope data from southeastern Spain with published data from selected Pb-Zn deposits in southern Europe (including Les Malines, L'Argentiere, and the Alpine, Iglesiente-Sulcis, and Montagne Noire districts) indicates the importance of a metasedimentary basement as a common source of ore Pb.

A novel methodology to investigate isotopic biosignatures

NASA Astrophysics Data System (ADS)

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

2012-04-01

An enduring goal of trace metal isotopic studies of Earth History is to find isotopic 'fingerprints' of life or of life's individual physiochemical processes. Generally, such signatures are sought by relating an isotopic effect observed in controlled laboratory conditions or a well-characterized environment to a more complex system or the geological record. However, such an approach is ultimately limited because life exerts numerous isotopic fractionations on any one element so it is hard to dissect the resultant net fractionation into its individual components. Further, different organisms, often with the same apparent cellular function, can express different isotopic fractionation factors. We have used a novel method to investigate the isotopic fractionation associated with a single physiological process-enzyme specific isotopic fractionation. We selected Cd isotopes since only one biological use of Cd is known, CdCA (a Cd/Zn carbonic anhydrase from the coastal diatom T. Weissflogii). Thus, our investigation can also inform the long standing mystery as to why this generally toxic element appears to have a nutrient-like dissolved isotopic and concentration profile in the oceans. We used the pET-15b plasmid to insert the CdCA gene into the E. coli genome. There is no known biochemical function for Cd in E. coli, making it an ideal vector for studying distinct physiological processes within a single organism. The uptake of Cd and associated isotopic fractionation was determined for both normal cells and those expressing CdCA. It was found that whole cells always exhibited a preference for the light isotopes of Cd, regardless of the expression of CdCA; adsorption of Cd to cell surfaces was not seen to cause isotopic fractionation. However, the cleaning procedure employed exerted a strong control on the observed isotopic composition of cells. Using existing protein purification techniques, we measured the Cd isotopic composition of different subcellular fractions of E. coli (e.g. membranes, cytosol, etc.), including the catalytic metal atoms within CdCA. These experiments allow isotopic exchange reactions to be observed in biological systems at an unparalleled resolution, demonstrating that isotopic fractionation can occur, in vivo, on length scales as small as a few Å. We will explore future applications of this technique using the marine geochemistry of Cd as a case study. This experimental approach has great promise for studying the individual isotopic biosignatures of other biochemical reactions, in particular those which may have been active during early Earth History.

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.

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.

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.

Sulfur isotopes of host strata for Howards Pass (Yukon–Northwest Territories) Zn-Pb deposits implicate anaerobic oxidation of methane, not basin stagnation

USGS Publications Warehouse

Johnson, Craig A.; Slack, John F.; Dumoulin, Julie A.; Kelley, Karen Duttweiler; Falck, Hendrik

2018-01-01

A new sulfur isotope stratigraphic profile has been developed for Ordovician-Silurian mudstones that host the Howards Pass Zn-Pb deposits (Canada) in an attempt to reconcile the traditional model of a stagnant euxinic basin setting with new contradictory findings. Our analyses of pyrite confirm the up-section 34S enrichment reported previously, but additional observations show parallel depletion of carbonate 13C, an increase in organic carbon weight percent, and a change in pyrite morphology. Taken together, the data suggest that the 34S enrichment reflects a transition in the mechanism of pyrite formation during diagenesis, not isotopic evolution of a stagnant water mass. Low in the stratigraphic section, pyrite formed mainly in the sulfate reduction zone in association with organic matter–driven bacterial sulfate reduction. In contrast, starting just below the Zn-Pb mineralized horizon, pyrite formed increasingly within the sulfate-methane transition zone in association with anaerobic oxidation of methane. Our new insights on diagenesis have implications for (1) the setting of Zn-Pb ore formation, (2) the reliability of redox proxies involving metals, and (3) the source of ore sulfur for Howards Pass, and potentially for other stratiform Zn-Pb deposits contained in carbonaceous strata.

Characterization and origin of low-T willemite (Zn2SiO4) mineralization: the case of the Bou Arhous deposit (High Atlas, Morocco)

NASA Astrophysics Data System (ADS)

Choulet, Flavien; Barbanson, Luc; Buatier, Martine; Richard, James; Vennemann, Torsten; Ennaciri, Aomar; Zouhair, Mohamed

2017-10-01

Willemite (Zn2SiO4) usually reported in hypogene non-sulfide deposits is described as the main ore mineral in the carbonate-hosted Bou Arhous zinc deposit. This deposit is located in the High Atlas intracontinental range that formed during the Tertiary. Based on a set of microscopic observations, it was possible to establish that willemite replaces primary sphalerite. On the basis of cathodoluminescence imaging, three successive generations of willemite are distinguished, with evidence of dissolution-reprecipitation processes. Willemite is also variably enriched in Ge (up to 1000 ppm), while Ge contents lower than 100 ppm are reported in the primary sulfide minerals. Depending on the willemite generation, this substitution was positively or negatively correlated to the Zn-Pb substitution. According to the nature of zoning (sector versus oscillatory), the incorporation of Ge was either controlled by crystallographic factors or by the nature of the mineralizing fluids. Willemite is associated with other oxidation-related mineral species, like cerussite (PbCO3) but is not in isotopic equilibrium and therefore not considered to be cogenetic. Oxygen isotope compositions support the formation of willemite at temperatures below 130 °C, from mixed meteoric and deeper, hydrothermal fluids. The formation of the High Atlas Belt during the Tertiary has contributed to the exhumation of the sulfide minerals and the development of vertical conduits for percolation of meteoric water and ascending hydrothermal fluids. In addition to a local contribution of silicate minerals of the host limestone, hydrothermal fluids probably transported Si and Ge that are incorporated in willemite.

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.

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

Liu, Shuling, E-mail: shulingliu@aliyun.com; College of Chemistry & Chemical Engineering, Shaanxi University of Science & Technology, Xi’an, Shaanxi 710021; Ma, Lanbing

Highlights: • ZnS/Ni{sub 2}P composites have been firstly synthesized via a gentle hydrothermal route. • The composites have been characterized by XRD, SEM and TEM. • ZnS/Ni{sub 2}P showed enhanced photocatalytic degradation activity for pyronine B. • The reason for the enhanced photocatalytic activity has been discussed. - Abstract: ZnS/Ni{sub 2}P core/shell composites were successfully synthesized using a hydrothermal method. The composites have been characterized by XRD, SEM, TEM and the corresponding results showed that the composites were composed of the cubic ZnS microspheres, which were made up of ZnS nanoparticles, and Ni{sub 2}P nanoparticles coated on the surfaces ofmore » ZnS microspheres. Compared with ZnS microspheres, ZnS/Ni{sub 2}P core/shell composites showed enhanced photocatalytic degradation activity for pyronine B under UV irradiation. This may be related to the effective separation of photogenerated electron–hole pairs in ZnS/Ni{sub 2}P composites which can greatly reduce the chance of their recombination. Furthermore, superoxide ions and hydroxyl radical can be more easily produced through ZnS/Ni{sub 2}P composites, which is also beneficial for the degradation of pyronine B.« less

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.

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.

Geochemical record of high emperor penguin populations during the Little Ice Age at Amanda Bay, Antarctica.

PubMed

Huang, Tao; Yang, Lianjiao; Chu, Zhuding; Sun, Liguang; Yin, Xijie

2016-09-15

Emperor penguins (Aptenodytes forsteri) are sensitive to the Antarctic climate change because they breed on the fast sea ice. Studies of paleohistory for the emperor penguin are rare, due to the lack of archives on land. In this study, we obtained an emperor penguin ornithogenic sediment profile (PI) and performed geochronological, geochemical and stable isotope analyses on the sediments and feather remains. Two radiocarbon dates of penguin feathers in PI indicate that emperor penguins colonized Amanda Bay as early as CE 1540. By using the bio-elements (P, Se, Hg, Zn and Cd) in sediments and stable isotope values (δ(15)N and δ(13)C) in feathers, we inferred relative population size and dietary change of emperor penguins during the period of CE 1540-2008, respectively. An increase in population size with depleted N isotope ratios for emperor penguins on N island at Amanda Bay during the Little Ice Age (CE 1540-1866) was observed, suggesting that cold climate affected the penguin's breeding habitat, prey availability and thus their population and dietary composition. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Two-proton transfer reactions on even Ni and Zn isotopes

NASA Astrophysics Data System (ADS)

Boucenna, A.; Kraus, L.; Linck, I.; Chan, Tsan Ung

1990-10-01

New levels strongly excited by 112-MeV 12C ions on even Ni and Zn isotopes are Jπ assigned on kinematical and geometrical arguments, crude shell-model calculations, and distorted-wave Born approximation angular-distribution analysis. These tentative assignments are supported by the Bansal-French model. Because of the contribution of additional collective effects, the two-proton transfer reaction spectra are less selectively fed than those obtained with the analogous two-neutron transfer reactions induced on the same targets in a similar energy range.

Single-neutron orbits near 78Ni: Spectroscopy of the N = 49 isotope 79Zn

DOE PAGES

Orlandi, R.; Mücher, D.; Raabe, R.; ...

2014-12-09

Single-neutron states in the Z=30, N=49 isotope 79Zn have been populated using the 78Zn(d, p) 79Zn transfer reaction at REX-ISOLDE, CERN. The experimental setup allowed the combined detection of protons ejected in the reaction, and of γ rays emitted by 79Zn. The analysis reveals that the lowest excited states populated in the reaction lie at approximately 1 MeV of excitation, and involve neutron orbits above the N=50 shell gap. From the analysis of γ -ray data and of proton angular distributions, characteristic of the amount of angular momentum transferred, a 5/2 + configuration was assigned to a state at 983more » keV. Comparison with large-scale-shell-model calculations supports a robust neutron N=50 shell-closure for 78Ni. Finally, these data constitute an important step towards the understanding of the magicity of 78Ni and of the structure of nuclei in the region.« less

The isotope composition of selenium in chondrites constrains the depletion mechanism of volatile elements in solar system materials

NASA Astrophysics Data System (ADS)

Vollstaedt, Hauke; Mezger, Klaus; Leya, Ingo

2016-09-01

Solar nebula processes led to a depletion of volatile elements in different chondrite groups when compared to the bulk chemical composition of the solar system deduced from the Sun's photosphere. For moderately-volatile elements, this depletion primarily correlates with the element condensation temperature and is possibly caused by incomplete condensation from a hot solar nebula, evaporative loss from the precursor dust, and/or inherited from the interstellar medium. Element concentrations and interelement ratios of volatile elements do not provide a clear picture about responsible mechanisms. Here, the abundance and stable isotope composition of the moderately- to highly-volatile element Se are investigated in carbonaceous, ordinary, and enstatite chondrites to constrain the mechanism responsible for the depletion of volatile elements in planetary bodies of the inner solar system and to define a δ 82 / 78 Se value for the bulk solar system. The δ 82 / 78 Se of the studied chondrite falls are identical within their measurement uncertainties with a mean of - 0.20 ± 0.26 ‰ (2 s.d., n = 14, relative to NIST SRM 3149) despite Se abundance depletions of up to a factor of 2.5 with respect to the CI group. The absence of resolvable Se isotope fractionation rules out a kinetic Rayleigh-type incomplete condensation of Se from the hot solar nebula or partial kinetic evaporative loss on the precursor material and/or the parent bodies. The Se depletion, if acquired during partial condensation or evaporative loss, therefore must have occurred under near equilibrium conditions to prevent measurable isotope fractionation. Alternatively, the depletion and cooling of the nebula could have occurred simultaneously due to the continuous removal of gas and fine particles by the solar wind accompanied by the quantitative condensation of elements from the pre-depleted gas. In this scenario the condensation of elements does not require equilibrium conditions to avoid isotope fractionation. The results further suggest that the processes causing the high variability of Se concentrations and depletions in ordinary and enstatite chondrites did not involve any measurable isotope fractionation. Different degrees of element depletions and isotope fractionations of the moderately-volatile elements Zn, S, and Se in ordinary and enstatite chondrites indicate that their volatility is controlled by the thermal stabilities of their host phases and not by the condensation temperature under canonical nebular conditions.

Mesoporous ZnS–NiS Nanocomposites for Nonenzymatic Electrochemical Glucose Sensors

PubMed Central

Wei, Chengzhen; Cheng, Cheng; Zhao, Junhong; Wang, Zhangtao; Wu, Haipeng; Gu, Kaiyue; Du, Weimin; Pang, Huan

2015-01-01

Mesoporous ZnS–NiS composites are prepared via ion- exchange reactions using ZnS as the precursor. The prepared mesoporous ZnS–NiS composite materials have large surface areas (137.9 m2 g−1) compared with the ZnS precursor. More importantly, the application of these mesoporous ZnS–NiS composites as nonenzymatic glucose sensors was successfully explored. Electrochemical sensors based on mesoporous ZnS–NiS composites exhibit a high selectivity and a low detection limit (0.125 μm) toward the oxidation of glucose, which can mainly be attributed to the morphological characteristics of the mesoporous structure with high specific surface area and a rational composition of the two constituents. In addition, the mesoporous ZnS–NiS composites coated on the surface of electrodes can be used to modify the mass transport regime, and this alteration can, in favorable circumstances, facilitate the amperometric discrimination between species. These results suggest that such mesoporous ZnS–NiS composites are promising materials for nonenzymatic glucose sensors. PMID:25861568

A carbon fiber-ZnS nanocomposite for dual application as an efficient cold cathode as well as a luminescent anode for display technology

NASA Astrophysics Data System (ADS)

Jha, Arunava; Sarkar, Sudipta Kumar; Sen, Dipayan; Chattopadhyay, K. K.

2015-01-01

In the current work we present a simple technique to develop a carbon nanofiber (CNF)/zinc sulfide (ZnS) composite material for excellent FED application. CNFs and ZnS microspheres were synthesized by following a simple thermal chemical vapor deposition and hydrothermal procedure, respectively. A rigorous chemical mixture of CNF and ZnS was prepared to produce the CNF-ZnS composite material. The cathodo-luminescence intensity of the composite improved immensely compared to pure ZnS, also the composite material showed better field emission than pure CNFs. For pure CNF the turn-on field was found to be 2.1 V μm-1 whereas for the CNF-ZnS composite it reduced to a value of 1.72 V μm-1. Altogether the composite happened to be an ideal element for both the anode and cathode of a FED system. Furthermore, simulation of our CNF-ZnS composite system using the finite element modeling method also ensured the betterment of field emission from CNF after surface attachment of ZnS nanoclusters.

Enhanced electrochemical performance of a ZnO-MnO composite as an anode material for lithium ion batteries.

PubMed

Song, Min Seob; Nahm, Sahn; Cho, Won Il; Lee, Chongmok

2015-09-28

A ZnO-MnO composite was synthesized using a simple solvothermal method combined with a high-temperature treatment. To observe the phase change during the heating process, in situ high-temperature XRD analysis was performed under vacuum conditions. The results indicated that ZnMn2O4 transformed into the ZnO-MnO composite phase starting from 500 °C and that this composite structure was retained until 700 °C. The electrochemical performances of the ZnO-MnO composite electrode were evaluated through galvanostatic discharge-charge tests and cyclic voltammetry analysis. Its initial coulombic efficiency was significantly improved to 68.3% compared to that of ZnMn2O4 at 54.7%. Furthermore, the ZnO-MnO composite exhibited improved cycling performance and enhanced rate capability compared with untreated ZnMn2O4. To clarify the discharge-charge mechanism of the ZnO-MnO composite electrode, the structural changes during the charge and discharge processes were also investigated using ex situ XRD and TEM.

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.

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.

Formation of an Isomeric State of Zn$sup 67$ by Bombardment with Slow Neutrons; FORMACION DE UN ESTADO ISOMERO DEL ZN$sup 67$$sub 30$ MEDIANTE BOMBARDEO CON NEUTRONES LENTOS

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

Montes Ponce De Leon, J.; Sanchez Del Rio, C.

1956-01-01

In this paper the identification of the isomeric state of Zn/sup 67/ by a new method is described. The isotopes Zn/sup 68/ and Zn/sup 67/ being both stable, the capture of slow neutrons by Zn/sup 68/ leads sometimes to the formation of the isomeric state of Zn/sup 67/; the state is identified by its half life, measured by delayed coincidences between the capture and the isomeric gamma rays. (auth)

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.

Oxygen and sulfur isotope systematics of sulfate produced during abiotic and bacterial oxidation of sphalerite and elemental sulfur

USGS Publications Warehouse

Balci, N.; Mayer, B.; Shanks, Wayne C.; Mandernack, K.W.

2012-01-01

Studies of metal sulfide oxidation in acid mine drainage (AMD) systems have primarily focused on pyrite oxidation, although acid soluble sulfides (e.g., ZnS) are predominantly responsible for the release of toxic metals. We conducted a series of biological and abiotic laboratory oxidation experiments with pure and Fe-bearing sphalerite (ZnS & Zn 0.88Fe 0.12S), respectively, in order to better understand the effects of sulfide mineralogy and associated biogeochemical controls of oxidation on the resultant ?? 34S and ?? 18O values of the sulfate produced. The minerals were incubated in the presence and absence of Acidithiobacillus ferrooxidans at an initial solution pH of 3 and with water of varying ?? 18O values to determine the relative contributions of H 2O-derived and O 2-derived oxygen in the newly formed sulfate. Experiments were conducted under aerobic and anaerobic conditions using O 2 and Fe(III) aq as the oxidants, respectively. Aerobic incubations with A. ferrooxidans, and S o as the sole energy source were also conducted. The ??34SSO4 values from both the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq produced sulfur isotope fractionations (??34SSO4-ZnS) of up to -2.6???, suggesting the accumulation of sulfur intermediates during incomplete oxidation of the sulfide. No significant sulfur isotope fractionation was observed from any of the aerobic experiments. Negative sulfur isotope enrichment factors (??34SSO4-ZnS) in AMD systems could reflect anaerobic, rather than aerobic pathways of oxidation. During the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq all of the sulfate oxygen was derived from water, with measured ?? 18OSO 4-H 2O values of 8.2??0.2??? and 7.5??0.1???, respectively. Also, during the aerobic oxidation of ZnS Fe and S o by A. ferrooxidans, all of the sulfate oxygen was derived from water with similar measured ?? 18OSO 4-H 2O values of 8.1??0.1??? and 8.3??0.3???, respectively. During biological oxidation of ZnS by O 2, an estimated 8% of sulfate-oxygen was derived from O 2, which is enriched in 18O relative to water, thus resulting in a larger apparent ?? 18OSO 4-H 2O value of 9.5???. Based on the data presented we hypothesize that the similar ?? 18OSO 4-H 2O values of ~8??? from all of the aerobic and anaerobic experiments result from a common rate-limiting step that involves oxygen isotopic exchange between a sulfite (SO3-) intermediate and H 2O. Our results indicate that the ??18OSO4 values cannot be used to distinguish biological and abiotic, nor aerobic versus anaerobic, pathways of sphalerite oxidation. However, the ?? 18OSO 4-H 2O values of ~8??? measured here are distinctly higher than ?? 18OSO 4-H 2O values of ~4??? previously reported for pyrite oxidation indicating the influence of sulfide mineralogy on measured ?? 18OSO 4 values. ?? 2011 Elsevier Ltd.

UV-light-assisted ethanol sensing characteristics of g-C3N4/ZnO composites at room temperature

NASA Astrophysics Data System (ADS)

Zhai, Jiali; Wang, Tao; Wang, Chuang; Liu, Dechen

2018-05-01

A highly efficient UV-light-assisted room temperature sensor based on g-C3N4/ZnO composites were prepared by an in situ precipitation method. The thermostability, composition, structure, and morphology properties of the as-prepared g-C3N4/ZnO composites were characterized by TGA, XRD, FT-IR, TEM, and XPS, respectively. And then, we studied the ethanol (C2H5OH) sensing performance of the g-C3N4/ZnO composites at the room temperature. Compared with pure ZnO and g-C3N4, the gas sensing activity of g-C3N4/ZnO composites was greatly improved at room temperature, for example, the g-C3N4/ZnO-8% composites showed an obvious response of 121-40 ppm C2H5OH at room temperature, which was 60 times higher than the pure ZnO based on the sensors under the same condition. The great enhancement of the C2H5OH sensing properties of composites can be understood by the efficient separation of photogenerated charge carriers of g-C3N4/ZnO heterogeneous and the UV-light catalytic effect. Finally, a possible mechanism for the gas sensing activity was proposed.

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

Liu, Shuling, E-mail: liusl8888@yahoo.com.cn; Li, Honglin; Yan, Lu

Graphical abstract: - Highlights: • 3D urchin-like ZnS/CdS composites were synthesized via a two-step method. • The CdS nanoparticles were assembled on the thorns of 3D ZnS urchins. • The ZnS/CdS composites show excellent photocatalytic degradation activities. • The modification of CdS on ZnS is responsible for the enhanced property. - Abstract: Urchin-like ZnS/CdS semiconductor composites were successfully synthesized by combining solvothermal route with homogeneous precipitation process. The as-obtained samples were characterized by means of XRD, EDX, TEM, HR-TEM, ED and FE-SEM techniques. The results show that the as-obtained composites were comprised of the hexagonal structure ZnS and CdS, andmore » CdS nanoparticles were assembled on the surfaces of the thorns of urchin-like ZnS. In addition, the optical properties and photocatalytic activities of the as-prepared ZnS/CdS composites toward some organic dyes (such as Methyl Orange, Pyronine B, Rhodamine B and Methylene Blue) were separately investigated. It is found that the ZnS/CdS composites exhibit excellent photocatalytic degradation activity for these dyes under UV irradiation, as compared to corresponding pure ZnS urchins and commercial anatase TiO{sub 2} (P-25). This enhanced activity may be related to the modification of CdS nanoparticles on the surfaces of thorns of ZnS urchins and a tentative mechanism for the enhanced photocatalytic degradation activities of the ZnS/CdS composite catalyst was proposed.« less

Anchoring ZnO Nanoparticles in Nitrogen-Doped Graphene Sheets as a High-Performance Anode Material for Lithium-Ion Batteries.

PubMed

Yuan, Guanghui; Xiang, Jiming; Jin, Huafeng; Wu, Lizhou; Jin, Yanzi; Zhao, Yan

2018-01-10

A novel binary nanocomposite, ZnO/nitrogen-doped graphene (ZnO/NG), is synthesized via a facile solution method. In this prepared ZnO/NG composite, highly-crystalline ZnO nanoparticles with a size of about 10 nm are anchored uniformly on the N-doped graphene nanosheets. Electrochemical properties of the ZnO/NG composite as anode materials are systematically investigated in lithium-ion batteries. Specifically, the ZnO/NG composite can maintain the reversible specific discharge capacity at 870 mAh g -1 after 200 cycles at 100 mA g -1 . Besides the enhanced electronic conductivity provided by interlaced N-doped graphene nanosheets, the excellent lithium storage properties of the ZnO/NG composite can be due to nanosized structure of ZnO particles, shortening the Li⁺ diffusion distance, increasing reaction sites, and buffering the ZnO volume change during the charge/discharge process.

Field-assisted sintering and phase transition of ZnS-CaLa 2S 4 composite ceramics

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

Li, Yiyu; Zhang, Lihua; Kisslinger, Kim

In the present study, zinc sulfide (ZnS) and calcium lanthanum sulfide (CaLa 2S 4, CLS) composite ceramics were consolidated via field-assisted sintering of 0.5ZnS-0.5CLS (volume ratio) composite powders at 800–1050 °C. Through sintering curve analyses and microstructural observations, it was determined that between 800 and 1000 °C, grain boundary diffusion was the main mechanism controlling grain growth for both the ZnS and CLS phases within the composite ceramics. The consolidated composite ceramics were determined to be composed of sphalerite ZnS, wurtzite ZnS and thorium phosphate CLS. The sphalerite-wurtzite phase transition of ZnS was further demonstrated to be accompanied by themore » formation of stacking faults and twins in the ceramics. Furthermore, it was also found that the addition of the CLS phase improved the indentation hardness of the ceramics relative to pure ZnS by homogeneous dispersion of ZnS and CLS small grains.« less

Field-assisted sintering and phase transition of ZnS-CaLa 2S 4 composite ceramics

DOE PAGES

Li, Yiyu; Zhang, Lihua; Kisslinger, Kim; ...

2017-07-17

In the present study, zinc sulfide (ZnS) and calcium lanthanum sulfide (CaLa 2S 4, CLS) composite ceramics were consolidated via field-assisted sintering of 0.5ZnS-0.5CLS (volume ratio) composite powders at 800–1050 °C. Through sintering curve analyses and microstructural observations, it was determined that between 800 and 1000 °C, grain boundary diffusion was the main mechanism controlling grain growth for both the ZnS and CLS phases within the composite ceramics. The consolidated composite ceramics were determined to be composed of sphalerite ZnS, wurtzite ZnS and thorium phosphate CLS. The sphalerite-wurtzite phase transition of ZnS was further demonstrated to be accompanied by themore » formation of stacking faults and twins in the ceramics. Furthermore, it was also found that the addition of the CLS phase improved the indentation hardness of the ceramics relative to pure ZnS by homogeneous dispersion of ZnS and CLS small grains.« less

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

Synthesis and characterization of polymer matrix composite material with combination of ZnO filler and nata de coco fiber as a candidate of semiconductor material

NASA Astrophysics Data System (ADS)

Saputra, Asep Handaya; Anindita, Hana Nabila

2015-12-01

Synthesis of semiconductor composite using acrylic matrix filled with ZnO and nata de coco fiber has been conducted in this research. The purpose of this research is to obtain semiconductor composite material that has a good mechanical strength and thermal resistance. In situ polymerization method is used in this research and the composites are ready to be characterized after 12 hours. The main parameter that is characterized is the electric conductivity of the composite. Additional parameters are also characterized such as composite's elastic modulus and glass transition temperature. The composites that has been made in this research can be classified as semiconductor material because the conductivity is in the range of 10-8-103 S/cm. In general the addition of ZnO and nata de coco filler can increase the conductivity of the composite. The highest semiconductor characteristic in acrylic/ZnO composite is obtained from 30% volume filler that reach 3.4 x 10-7 S/cm. Similar with acrylic/ZnO composite, in acrylic/nata de coco fiber composite the highest semiconductor characteristic is also obtained from 30% volume filler that reach 1.15 x 10-7 S/cm. Combination of 20% volume of ZnO, 10% volume of nata de coco, and 70% volume of acrylic resulting in composite with electric conductivity of 1.92 x 10-7 S/cm. In addition, combination of ZnO and nata de coco fiber as filler in composite can also improve the characteristic of composite where composite with 20% volume of ZnO filler and 10% volume of nata de coco fiber resulting in composite with elastic modulus of 1.79 GPa and glass transition temperature of 175.73°C which is higher than those in acrylic/ZnO composite.

Two-proton transfer reactions on even Ni and Zn isotopes

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

Boucenna, A.; Kraus, L.; Linck, I.

New levels strongly excited by 112-MeV {sup 12}C ions on even Ni and Zn isotopes are {ital J}{sup {pi}} assigned on kinematical and geometrical arguments, crude shell-model calculations, and distorted-wave Born approximation angular-distribution analysis. These tentative assignments are supported by the Bansal-French model. Because of the contribution of additional collective effects, the two-proton transfer reaction spectra are less selectively fed than those obtained with the analogous two-neutron transfer reactions induced on the same targets in a similar energy range.

Trace determination of zinc by substoichiometric isotope dilution analysis

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

Sandhya, D.; Priya, S.; Subramanian, M.O.S.

1996-09-01

A radiometric method based on substoichiometric isotope dilution analysis using 1,10-phenanthroline and a substoichiometric amount of eosin was developed for determining trace amounts of zinc. Evaluation of various metal ion interferences shows that as little as 0.2 {mu}g Zn could be determined in an aqueous-phase volume of 60 mL. The method has been successfully applied to the determination of Zn in city waste incineration ash, cadmium metal, Fourts-B tablets, Boro-plus ointment, and magnesium alloy samples. 12 refs., 3 figs., 3 tabs.

Boron doped ZnO embedded into reduced graphene oxide for electrochemical supercapacitors

NASA Astrophysics Data System (ADS)

Alver, Ü.; Tanrıverdi, A.

2016-08-01

In this work, reduced graphene oxide/boron doped zinc oxide (RGO/ZnO:B) composites were fabricated by a hydrothermal process and their electrochemical properties were investigated as a function of dopant concentration. First, boron doped ZnO (ZnO:B) particles was fabricated with different boron concentrations (5, 10, 15 and 20 wt%) and then ZnO:B particles were embedded into RGO sheets. The physical properties of sensitized composites were characterized by XRD and SEM. Characterization indicated that the ZnO:B particles with plate-like structure in the composite were dispersed on graphene sheets. The electrochemical properties of the RGO/ZnO:B composite were investigated through cyclic voltammetry, galvanostatic charge/discharge measurements in a 6 M KOH electrolyte. Electrochemical measurements show that the specific capacitance values of RGO/ZnO:B electrodes increase with increasing boron concentration. RGO/ZnO:B composite electrodes (20 wt% B) display the specific capacitance as high as 230.50 F/g at 5 mV/s, which is almost five times higher than that of RGO/ZnO (52.71 F/g).

Soil geochemical survey of abandoned mining sites in the Eastern-Central Peloritani Mountains, Sicily, Italy

USGS Publications Warehouse

Consenza, A.; Lima, A.; Ayuso, Robert A.; Foley, Nora K.; Albanese, S.; Messina, A.; De Vivo, B.

2015-01-01

This investigation focused on topsoils (n = 122) and vertical profiles (n = 6) distributed over an area of 250 km2 in the eastern-central Peloritani Mountains, northeastern Sicily. Georeferenced concentration of 53 elements (including potentially harmful ones), determined by ICP-MS after an aqua regia leach, were used to produce geochemical maps by means of a GIS-aided spatial interpolation process. Results show that there are two distinct areas: the larger, located between the Fiumendinisi, Budali and Ali villages, and the other between C. Postlioni and Femmina Morta, which contain anomalous As (up to 727 mg/kg), Sb (up to 60 mg/kg), Ag (up to 1 mg/kg) and Au (up to 0.1 mg/kg) concentrations. Most of the investigated areas have high contamination levels for As, Zn, Sb, and Pb that exceed the threshold values (As = 20 mg/kg, Zn = 150 mg/kg, Sb = 10 mg/kg and Pb = 100 mg/kg) established for soils by the Italian Environmental Law (Decreto Legislativo 2006, number 152).The isotopic ratios of 206Pb/207Pb and 208Pb/207Pb have been measured in selected soils on both leaches [using 1M HNO3–1.75M HCl (50:50)] and residues thereof. Soil leach reflects possible anthropogenic contamination, whereas soil residues indicate geogenic contributions. Results suggest that most of contamination in the soils is related to the presence of sulphide and sulphosalt rock-forming minerals in the surveyed area. The soil fraction contains a Pb value >1600 mg/kg and has ratios of 1.1695 for 206Pb/207Pb and 2.4606 for 208Pb/207Pb. Only one soil leach isotopic composition could reflect possible anthropogenic contamination. The correlation among As, Zn, Pb contents v. Pb isotopic signatures of 206Pb/207Pb indicates that surface and deep soils collected from profiles are dominated by geogenic compositions.

Preparation of ZnS/ZnO core - Shell nanocomposite and its photocatalytic behaviour for dye degradation

NASA Astrophysics Data System (ADS)

Patil, Bharati N.; Acharya, Smita A.

2018-05-01

In the present work ZnS-ZnO core-shell-type composite nanostructures was prepared by hydrothermal method. The prepared samples were characterized by X-ray diffraction (XRD) for structural confirmation. Microstructural study by scanning electron microscopy (SEM) exhibit nanoscale dimensions of as-synthesized composite. UV/VIS spectra were recorded for evaluation of photophysical properties. The composite was explored as photocatalysts to study dye degradation using methylene blue in aqueous slurry under irradiation of 663 nm wavelength and congo red under irradiation of 493 nm wavelength. Under the same conditions the photocatalytic activity of the individual phases ZnS and ZnO were also examined, just for sake of comparison. The ZnS-ZnO composite is found to be enhancing the rate of photo degradation of toxic dyes in presence of visible light as compared to ZnS and ZnO individual phases. Thus ZnS based metal sulphide/oxide semiconductor nanocomposites are potential material for Photo-degradation of toxic dyes, and act as good photocatalyst.

Dielectric and varistor properties of rare-earth-doped ZnO and CaCu3Ti4O12 composite ceramics

NASA Astrophysics Data System (ADS)

Lu, Huafei; Lin, Yuanhua; Yuan, Jiancong; Nan, Cewen; Chen, Kexin

2013-02-01

To investigate the multi-functional ceramics with both high permittivity and large nonlinear coefficient, we have prepared rare-earth Tb-and-Co doped ZnO and TiO2-rich CaCu3Ti4O12 (TCCTO) powders by chemical co-precipitation and sol-gel methods respectively, and then obtained the TCCTO/ZnO composite ceramics, sintered at 1100°C for 3 h in air. Analyzing the composite ceramics of the microstructure and phase composition indicated that the composite ceramics were composed of the main phases of ZnO and CaCu3Ti4O12 (CCTO). Our results revealed that the TCCTO/ZnO composite ceramics showed both high dielectric and good nonlinear electrical behaviors. The composite ceramic of TCCTO: ZnO = 0.3 exhibited a high dielectric constant of 210(1 kHz) with a nonlinear coefficient of 11. The dielectric behavior of TCCTO/ZnO composite could be explained by the mixture rule. With the high dielectric permittivity and tunable varistor behaviors, the composite ceramics has a potential application for the higher voltage transportation devices.

Ca:Mg:Zn:CO3 and Ca:Mg:CO3-tri- and bi-elemental carbonate microparticles for novel injectable self-gelling hydrogel-microparticle composites for tissue regeneration.

PubMed

Douglas, Timothy E L; Sobczyk, Katarzyna; Łapa, Agata; Włodarczyk, Katarzyna; Brackman, Gilles; Vidiasheva, Irina; Reczyńska, Katarzyna; Pietryga, Krzysztof; Schaubroeck, David; Bliznuk, Vitaliy; Voort, Pascal Van Der; Declercq, Heidi A; Bulcke, Jan Van den; Samal, Sangram Keshari; Khalenkow, Dmitry; Parakhonskiy, Bogdan V; Van Acker, Joris; Coenye, Tom; Lewandowska-Szumieł, Małgorzata; Pamuła, Elżbieta; Skirtach, Andre G

2017-03-24

Injectable composites for tissue regeneration can be developed by dispersion of inorganic microparticles and cells in a hydrogel phase. In this study, multifunctional carbonate microparticles containing different amounts of calcium, magnesium and zinc were mixed with solutions of gellan gum (GG), an anionic polysaccharide, to form injectable hydrogel-microparticle composites, containing Zn, Ca and Mg. Zn and Ca were incorporated into microparticle preparations to a greater extent than Mg. Microparticle groups were heterogeneous and contained microparticles of differing shape and elemental composition. Zn-rich microparticles were 'star shaped' and appeared to consist of small crystallites, while Zn-poor, Ca- and Mg-rich microparticles were irregular in shape and appeared to contain lager crystallites. Zn-free microparticle groups exhibited the best cytocompatibility and, unexpectedly, Zn-free composites showed the highest antibacterial activity towards methicilin-resistant Staphylococcus aureus. Composites containing Zn-free microparticles were cytocompatible and therefore appear most suitable for applications as an injectable biomaterial. This study proves the principle of creating bi- and tri-elemental microparticles to induce the gelation of GG to create injectable hydrogel-microparticle composites.

Effects of plasmonic field due to gold nanoparticles and magnetic field on photocurrents of zinc porphyrin-viologen linked compound-gold nanoparticle composite films

NASA Astrophysics Data System (ADS)

Yonemura, Hiroaki; Niimi, Tomoki; Yamada, Sunao

2016-03-01

Composite films of zinc-porphyrin-viologen (ZnP-V2+) linked compound containing six methylene group [ZnP(6)V]-gold nanoparticles (AuNP) were fabricated by combining electrostatic layer-by-layer adsorption and the Langmuir-Blodgett method. The anodic photocurrents of the ZnP(6)V-AuNP composite films are higher than those of the ZnP(6)V films. The large photocurrents in ZnP(6)V-AuNP composite films are most likely attributable to the combination of localized surface plasmon resonance due to AuNP and photoinduced intramolecular electron transfer from excited state of ZnP to V2+. The photocurrents of the ZnP(6)V-AuNP composite films increase in the presence of magnetic field. The photocurrents increase with low magnetic fields (B ≤ 150 mT) and are almost constant under high magnetic fields (B ≥ 150 mT). Magnetic field effects (MFEs) were clearly observed for both ZnP(6)V-AuNP composite films and ZnP(6)V films. The MFEs can be explained by a radical pair mechanism.

Geochemistry and origin of regional dolomites. Final report

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

Hanson, G.N.; Meyers, W.J.

1995-05-01

The main goal of our research on dolomites has been to better understand the composition of the fluids and processes of the fluid-rock interaction responsible for the formation of massive dolostones occurring over regional scales within sedimentary sequences. Understanding the timing of dolomitization, the fluids responsible for the dolomitization and the timing of the development of porosity has major economic ramifications in that dolomites are major oil reservoirs often having better reservoir properties than associated limestones. Our approach has been to apply trace element, major element, petrographic, crystallographic, stable isotope and radiogenic isotope systems to test models for the originsmore » of dolomites and to give information that may allow us to develop new models. Fluid compositions and processes are evaluated through the use of numerical models which we have developed showing the simultaneous evolution of the trace element and isotope systems during dolomitization. Our research has included the application of B, O, C, Sr, Nd and Pb isotope systematics and the trace elements Mn, Fe St, rare earth elements, Rb, Ba, U, Th, Pb, Zn, Na, Cl, F and SO{sub 4}{sup 2-}. Analyses are possible on individual cements or dolomite types using micro-sampling or microprobe techniques. The microprobe techniques used include synchrotron X-ray microprobe analysis at Brookhaven National Laboratory or electron microprobe at Stony Brook. Lack of a modern analogue for ancient massive dolostones has limited the application of the uniformitarian concept to developing models for the ancient regional dolostones. In addition it has not been possible to synthesize dolomite in the laboratory under conditions similar to the sedimentary or diagenetic possible environments in which the dolomites must have formed.« less

A geochemical study of Nea-Kameni hyalodacites (Santorini Volcano, Aegean island arc). Inferences concerning the origin and effects of solfataras and magmatic evolution

NASA Astrophysics Data System (ADS)

Briqueu, Louis; Lancelot, Joël R.

1984-03-01

Since the Santorini Volcano (Aegean arc, eastern Mediterranean Sea) collapsed, volcanic activity has been located at the center of the flooded caldera. Over the past 800 years, five lava flows have formed one of the central islets (Nea-Kameni). Since 1951, when the last eruption occurred, a permanent fumarolic activity has remained. We present chemical analyses (major elements, trace-elements and Sr isotopic ratios) of ten samples from the five hyalodacitic lava flows, showing different stages of alteration, from a completely fresh lava up to one bearing native sulfur and other sublimates. Only the macroscopic aspect of these hyalodacites is affected by fumarolic activity. The elements that are mobile as a result of hydrothermal processes, such as the alkaline (K, Rb) or the chalcophile elements (Zn, Pb), show great homogeneity; the same can be said for the Sr isotopic compositions which range from 0.7046 to 0.7049. None of the analyzed samples has an Sr isotopic composition as high as those reported by Puchelt and Hoefs (1971) for rock samples collected in the same lava flows. If we take into account the marine surroundings of Nea-Kameni islet, these observations put severe restraints on the different hypotheses regarding the origin of the halogens (seawater or meteoric water). The contamination processes of these dacitic lavas are clearly less important than assumed by other authors according to previous Sr isotopic data. Finally, the homogeneity of the elements with low partition coefficients is sufficient to show that the magma has not undergone any perceptible evolution during the last 300 years.

Investigating nuclear shell structure in the vicinity of 78Ni: Low-lying excited states in the neutron-rich isotopes Zn,8280

NASA Astrophysics Data System (ADS)

Shiga, Y.; Yoneda, K.; Steppenbeck, D.; Aoi, N.; Doornenbal, P.; Lee, J.; Liu, H.; Matsushita, M.; Takeuchi, S.; Wang, H.; Baba, H.; Bednarczyk, P.; Dombradi, Zs.; Fulop, Zs.; Go, S.; Hashimoto, T.; Honma, M.; Ideguchi, E.; Ieki, K.; Kobayashi, K.; Kondo, Y.; Minakata, R.; Motobayashi, T.; Nishimura, D.; Otsuka, T.; Otsu, H.; Sakurai, H.; Shimizu, N.; Sohler, D.; Sun, Y.; Tamii, A.; Tanaka, R.; Tian, Z.; Tsunoda, Y.; Vajta, Zs.; Yamamoto, T.; Yang, X.; Yang, Z.; Ye, Y.; Yokoyama, R.; Zenihiro, J.

2016-02-01

The low-lying level structures of nuclei in the vicinity of 78Ni were investigated using in-beam γ -ray spectroscopy to clarify the nature of the nuclear magic numbers Z =28 and N =50 in systems close to the neutron drip line. Nucleon knockout reactions were employed to populate excited states in 80Zn and 82Zn. A candidate for the 41+ level in 80Zn was identified at 1979(30) keV, and the lifetime of this state was estimated to be 136-67+92 ps from a line-shape analysis. Moreover, the energy of the 21+ state in 82Zn is reported to lie at 621(11) keV. The large drop in the 21+ energy at 82Zn indicates the presence of a significant peak in the E (21+) systematics at N =50 . Furthermore, the E (41+) /E (21+) and B (E 2 ;41+→21+) /B (E 2 ;21+→0g.s . +) ratios in 80Zn were deduced to be 1.32 (3 ) and 1 .12-60+80 , respectively. These results imply that 80Zn can be described in terms of two-proton configurations with a 78Ni core and are consistent with a robust N =50 magic number along the Zn isotopic chain. These observations, therefore, indicate a persistent N =50 shell closure in nuclei far from the line of β stability, which in turn suggests a doubly magic structure for 78Ni.

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.

Solution processable RGO-CdZnS composite for solar light responsive photocatalytic degradation of 4-Nitrophenol

NASA Astrophysics Data System (ADS)

Ibrahim, Sk; Chakraborty, Koushik; Pal, Tanusri; Ghosh, Surajit

2017-05-01

We report the one pot single step synthesis and characterization of solution processable reduced graphene oxide (RGO) - cadmium zinc sulfide (CdZnS) nanocomposite materials. The composite was characterized structurally and morphologically by XRD and TEM studies. The reduction of GO in RGO-CdZnS composite, was confirmed by XPS and Raman spectroscopy. The photocatalytic activity of the RGO-CdZnS composite was investigated towards the degradation of 4-Nitrophenol. A notable increase of photocatalytic efficiency of RGO-CdZnS compare to controlled CdZnS was observed. Here RGO plays a crucial role to efficient photo induced charge separation from the CdZnS, and decreases the electron-hole recombination probability and subsequently enhanced the photocatalytic activity of the RGO-CdZnS composite material under simulated solar light irradiation. This work highlights the potential application of RGO-based materials in the field of photocatalytic degradation of organic water pollutant.

Improved luminescence intensity and stability of thermal annealed ZnO incorporated Alq3 composite films.

PubMed

Cuba, M; Muralidharan, G

2015-11-01

The 30 wt% of ZnO (weight percentage of ZnO has been optimised) incorporated tris- (8-hydroxyquinoline)aluminum (Alq3) has been synthesised and coated on to glass substrates using dip coating method. The structural and optical properties of the Alq3/ZnO composite film after thermal annealing from 50 to 300 °C insteps 50° has been studied and reported. XRD pattern reveals the presence of crystalline ZnO in all the annealed films. The films annealed above 150 °C reveal the presence of crystalline Alq3 along with crystalline ZnO. The FTIR spectra confirm the presence of hydroxyquinoline and ZnO vibration in all the annealed composite films. The composite films annealed above 150 °C show a partial sublimation and degradation of hydroxyquinoline compounds. The ZnO incorporated composite films (Alq3/ZnO) exhibit two emission peaks, one corresponding to ZnO at 487 nm and another at 513 nm due to Alq3. The films annealed at 200 °C exhibit maximum photoluminescence (PL) intensity than pristine film at 513 nm when excited at 390 nm.

Structural Characterization and Antifungal Studies of Zinc-Doped Hydroxyapatite Coatings.

PubMed

Iconaru, Simona Liliana; Prodan, Alina Mihaela; Buton, Nicolas; Predoi, Daniela

2017-04-09

The present study is focused on the synthesis, characterization and antifungal evaluation of zinc-doped hydroxyapatite (Zn:HAp) coatings. The Zn:HAp coatings were deposited on a pure Si (Zn:HAp_Si) and Ti (Zn:HAp_Ti) substrate by a sol-gel dip coating method using a zinc-doped hydroxyapatite nanogel. The nature of the crystal phase was determined by X-ray diffraction (XRD). The crystalline phase of the prepared Zn:HAp composite was assigned to hexagonal hydroxyapatite in the P6 3/m space group. The colloidal properties of the resulting Zn:HAp (x Zn = 0.1) nanogel were analyzed by Dynamic Light Scattering (DLS) and zeta potential. Scanning Electron Microscopy (SEM) was used to investigate the morphology of the zinc-doped hydroxyapatite (Zn:HAp) nanogel composite and Zn:HAp coatings. The elements Ca, P, O and Zn were found in the Zn:HAp composite. According to the EDX results, the degree of Zn substitution in the structure of Zn:HAp composite was 1.67 wt%. Moreover, the antifungal activity of Zn:HAp_Si and Zn:HAp_Ti against Candida albicans ( C. albicans ) was evaluated. A decrease in the number of surviving cells was not observed under dark conditions, whereas under daylight and UV light illumination a major decrease in the number of surviving cells was observed.

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.

Tracing of ca 800 yr old mining activity in peat bog using Pb elemental concentrations and isotope compositions.

NASA Astrophysics Data System (ADS)

Baron, S.; Carignan, J.; Ploquin, A.

2003-04-01

Sixty sites of slags have been documented on the Mont-Lozère in southern France. The petrographic analysis shows that slags are metallurgical wastes (800 to 850 yr BP) which certainly result from smelting activity for lead and silver extraction (Ploquin et al., 2001). The aims of this study are: 1) to trace the source of Pb ores which supplied the smelting sites, by using the Pb isotopic composition of several surrounding Pb deposits, 2) to evaluate the actual pollution caused by these slags, by using elemental and isotopic compositions of soils, water and vegetation, and 3) to document the pollution history of the region, by using elemental and isotopic compositions of peat bog cores collected in the neighbourhood of the historical smelting sites. The lead isotopic composition of galena collected in most surrounding ores is very similar to that of different slag samples. On the other hand, the high precision of the results allowed us to select the mineralised areas which were probably the ore sources. The Pb isotopic composition of slags is even more homogeneous: 208/206 Pb: 2.092±0.002; 206/207 Pb: 1.179±0.001; 208/204 Pb: 38.663±0.025; 207/204 Pb: 15.665±0.006; 206/204 Pb: 18.476±0.023, and will allow source tracing in the environment. The "Narses Mortes" peat bog, around which two smelting sites have been reported, is strongly minerotrophic and contains 8 to 60% ash. A 1.40 m core have been retrieved and divided into 58 individual samples. Minerotrophic peat bog records both atmospheric deposition, soils leaching and the grounwater influence. The measured metal concentrations are normalised to Al contents of peat bog samples and the metal/Al ratios are compared to that of the Mont-Lozère granite: relative excess in metal concentrations are found in peat bog samples. An increasing excess of most metals (Pb, Zn, Cd...) was measured for surface samples, from 55 cm depth to the top of the core (23 cm depth). This profil might be attributed to atmospheric input during the last centuries. Pb and As alone are also enriched in some deeper samples (between 120--90 cm depth). At the moment, no sedimentation rates are available for this section of the peat bog. However, according to palynological data (de Beaulieu, in progress), the bottom of the core might be as old as 5000 years BP. This would place the medieval activities at the base of the surface metal enrichment (˜55 cm depth), having no large effect in Pb concentrations measured in peat bog. The older Pb-As enrichment remain enigmatic and may correspond to earlier anthropogenic activities (2000--2500 BP), a period for which very few traces of metallurgical activities are found in Occidental Europe. 14C dating and Pb isotope works are going on peat bog samples trying to discriminate metals sources.

In vitro corrosion behavior and in vivo biodegradation of biomedical β-Ca3(PO4)2/Mg-Zn composites.

PubMed

Yu, Kun; Chen, Liangjian; Zhao, Jun; Li, Shaojun; Dai, Yilong; Huang, Qiao; Yu, Zhiming

2012-07-01

In this study 5, 10 and 15% β-Ca(3)(PO(4))(2)/Mg-Zn composites were prepared through powder metallurgy methods, and their corrosion behavior and mechanical properties were studied in simulated body fluid (SBF) at 37°C. The 10% β-Ca(3)(PO(4))(2)/Mg-Zn composite was selected for cytocompatibility assessment and in vivo biodegradation testing. The results identified the α-Mg, MgZn and β-Ca(3)(PO(4))(2) phases in these sintered composites. The density and elastic modulus of the β-Ca(3)(PO(4))(2)/Mg-6% Zn composite match those of natural bone, and the strength is approximately double that of natural bone. The 10% β-Ca(3)(PO(4))(2)/Mg-6% Zn composites exhibit good corrosion resistance, as determined by a 30 day immersion test and electrochemical measurements in SBF at 37°C. The 10% β-Ca(3)(PO(4))(2)/Mg-6% Zn composite is safe for cellular applications, with a cytotoxicity grade of ∼0-1 against L929 cells in in vitro testing. The β-Ca(3)(PO(4))(2)/Mg-6% Zn composite also exhibits good biocompatibility with the tissue and the important visceral organs the heart, kidney and liver of experimental rabbits. The composite has a suitable degradation rate and improves the concrescence of a pre-broken bone. The corrosion products, such as Mg(OH)(2) and Ca(5)(PO(4))(6)(OH)(2), can improve the biocompatibility of the β-Ca(3)(PO(4))(2)/Mg-Zn composite. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Thallium isotope variations in anthropogenically-affected soils

NASA Astrophysics Data System (ADS)

Vanek, Ales; Chrastny, Vladislav; Penizek, Vit; Mihaljevic, Martin; Komarek, Michael; Cabala, Jerzy

2014-05-01

Our preliminary data from soils impacted by long-term Tl deposition in the vicinity of a primary/secondary Zn smelter at Olkusz (Poland) indicate apparent variability of ɛ205Tl within soil profiles. The identified ɛ205Tl values presented for the forest soil profile reached -1.7 in the surface/organic horizon, +1.9 in the organo-mineral horizon (Ap), and +1.0 in the mineral horizon (C). This finding suggests both the enrichment of 203Tl isotope in the topsoil, as well as its preferential release during smelting operations, as "lighter" Tl tends to enter the emissions during a high-temperature process. The maximum ɛ205Tl value in the subsurface horizon Ap is in accordance with the concentration peak of oxalate-extractable Mn, indicating the presence of amorphous/poorly-crystalline Mn oxides with a potential to isotopically fractionate Tl toward the "heavier" fraction. The Tl isotope signature in the bottom horizon probably reflects the composition of a local geochemical anomaly of Tl. However, a portion of mobile (anthropogenic) Tl with negative ɛ205Tl moving downwards in the soil profile cannot be neglected. In general, there is no detailed information about the biogeochemical cycling and variations of Tl isotopes in areas affected by significant anthropogenic inputs of the metal (e.g., coal burning and primary metallurgy); the questions of the degree to which the factors such as soil (and sediment) chemistry, mineralogy, local biota, and pollution source control Tl isotope fractionation remain unresolved. Therefore, further research on the topic is needed before any principal conclusions will be made.

Amplified spontaneous emission from ZnO in n-ZnO/ZnO nanodots-SiO(2) composite/p-AlGaN heterojunction light-emitting diodes.

PubMed

Shih, Ying Tsang; Wu, Mong Kai; Li, Wei Chih; Kuan, Hon; Yang, Jer Ren; Shiojiri, Makoto; Chen, Miin Jang

2009-04-22

This study demonstrates amplified spontaneous emission (ASE) of the ultraviolet (UV) electroluminescence (EL) from ZnO at lambda~380 nm in the n-ZnO/ZnO nanodots-SiO(2) composite/p- Al(0.12)Ga(0.88)N heterojunction light-emitting diode. A SiO(2) layer embedded with ZnO nanodots was prepared on the p-type Al(0.12)Ga(0.88)N using spin-on coating of SiO(2) nanoparticles followed by atomic layer deposition (ALD) of ZnO. An n-type Al-doped ZnO layer was deposited upon the ZnO nanodots-SiO(2) composite layer also by the ALD technique. High-resolution transmission electron microscopy (HRTEM) reveals that the ZnO nanodots embedded in the SiO(2) matrix have diameters of 3-8 nm and the wurtzite crystal structure, which allows the transport of carriers through the thick ZnO nanodots-SiO(2) composite layer. The high quality of the n-ZnO layer was manifested by the well crystallized lattice image in the HRTEM picture and the low-threshold optically pumped stimulated emission. The low refractive index of the ZnO nanodots-SiO(2) composite layer results in the increase in the light extraction efficiency from n-ZnO and the internal optical feedback of UV EL into n-ZnO layer. Consequently, significant enhancement of the UV EL intensity and super-linear increase in the EL intensity, as well as the spectral narrowing, with injection current were observed owing to ASE in the n-ZnO layer.

Genetic and geochemical signatures to prevent frauds and counterfeit of high-quality asparagus and pistachio.

PubMed

Zannella, Carmela; Carucci, Francesca; Aversano, Riccardo; Prohaska, Thomas; Vingiani, Simona; Carputo, Domenico; Adamo, Paola

2017-12-15

A fingerprinting strategy based on genetic (simple sequence repeat) and geochemical (multielement and 87 Sr/ 86 Sr ratio) analysis was tested to prove the geographical origin of high-quality Italian products "White Asparagus from Bassano del Grappa" and "Green Pistachio from Bronte". Genetic analysis generated many polymorphic alleles and different specific amplified fragments in both agriproducts. In addition, a core set of markers was defined. According to variability within production soils and products, potential candidate elements linking asparagus (Zn, P, Cr, Mg, B, K) and pistachio (Mn, P, Cr, Mg, Ti, B, K, Sc, S) to the production areas were identified. The Sr isotopic signature was an excellent marker when Italian asparagus was compared with literature data for Hungarian and Peruvian asparagus. This work reinforces the use of Sr isotope composition in the soil bioavailable fraction, as assessed by 1mol/L NH 4 NO 3 , to distinguish white asparagus and pistachio originating from different geographical areas. Copyright © 2017 Elsevier Ltd. All rights reserved.

Cellular proliferation, cellular viability, and biocompatibility of HA-ZnO composites.

PubMed

Saha, Naresh; Dubey, Ashutosh K; Basu, Bikramjit

2012-01-01

One of the important issues in the development of hydroxyapatite (HA)-based biomaterials is the prosthetic infection, which limits wider use of monolithic HA despite superior cellular response. Recently, we reported that ZnO addition to HA can induce bactericidal property. It is therefore important to assess how ZnO addition influences the cytotoxicity property and cell adhesion/proliferation on HA-ZnO composite surfaces in vitro. In the above perspective, the objective of this study is to investigate the cell type and material composition dependent cellular proliferation and viability of pressureless sintered HA-ZnO composites. The combination of cell viability data as well as morphological observations of cultured human osteoblast-like SaOS2 cells and mouse fibroblast L929 cells suggests that HA-ZnO composites containing 10 Wt % or lower ZnO exhibit the ability to support cell adhesion and proliferation. Both SaOS2 and L929 cells exhibit extensive multidirectional network of actin cytoskeleton and cell flattening on the lower ZnO containing (≤10 Wt %) HA-ZnO composites. The in vitro results illustrate how variation in ZnO content can influence significantly the cell vitality, as evaluated using MTT biochemical assay. Also, the critical statistical analysis reveals that ZnO addition needs to be carefully tailored to ensure good in vitro cytocompatibility. The underlying reasons for difference in biological properties are analyzed. It is suggested that surface wettability as well as dissolution of ZnO, both contribute to the observed differences in cellular viability and proliferation. Copyright © 2011 Wiley Periodicals, Inc.

Composite tin and zinc oxide nanocrystalline particles for enhanced charge separation in sensitized degradation of dyes.

PubMed

Bandara, J; Tennakone, K; Jayatilaka, P P B

2002-10-01

Composite ZnO/SnO2 catalyst has been studied for the sensitized degradation of dyes e.g. Eosin Y (2', 4', 5', 7'-tetrabromofluorescein disodium salt) in relation to efficient charge separation properties of the catalyst. Improved photocatalytic activity was observed in the case of ZnO/SnO2 composite catalyst compared to the catalytic activity of ZnO, SnO2 or TiO2 powder. The suppression of charge recombination in the composite ZnO/SnO2 catalyst led to higher catalytic activity for the degradation of Eosin Y. Degradation of Eosin follows concomitant formation of CO2 and formation of CO2 followed a pseudo-first-order rate. Photoelectrochemical cells constructed using SnO2, ZnO, ZnO/SnO2 sensitized with Eosin Y showed V(oc) of 175, 306, 512 mV/cm2 and I(sc) of 50, 70, 200 microA/cm2 respectively. A higher irreversible degradation of Eosin Y and higher V(oc) observed on composite ZnO/SnO2 than ZnO and SnO2 separately can be considered as a proof of enhanced charge separation of ZnO/SnO2 catalyst. Eosin Y showed a higher emission decreases on ZnO/SnO2 composite than on individual ZnO, SnO2 or TiO2 indicating dominance of the charge injection process. Photoinjected electrons are tunneled from ZnO to SnO2 particles accumulating injected electrons in the conduction bands allowing wider separation of excited carriers.

Low Working-Temperature Acetone Vapor Sensor Based on Zinc Nitride and Oxide Hybrid Composites.

PubMed

Qu, Fengdong; Yuan, Yao; Guarecuco, Rohiverth; Yang, Minghui

2016-06-01

Transition-metal nitride and oxide composites are a significant class of emerging materials that have attracted great interest for their potential in combining the advantages of nitrides and oxides. Here, a novel class of gas sensing materials based on hybrid Zn3 N2 and ZnO composites is presented. The Zn3 N2 /ZnO (ZnNO) composites-based sensor exhibits selectivity and high sensitivity toward acetone vapor, and the sensitivity is dependent on the nitrogen content of the composites. The ZnNO-11.7 described herein possesses a low working temperature of 200 °C. The detection limit (0.07 ppm) is below the diabetes diagnosis threshold (1.8 ppm). In addition, the sensor shows high reproducibility and long-term stability. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural and photocatalytic studies on pure and Sn ion doped ZnO-graphene nanocomposites

NASA Astrophysics Data System (ADS)

Beura, Rosalin; Thangadurai, P.

2016-05-01

Graphene based metal oxide nanocomposites have been widely used as a photocatalyst for the treatment of water pollutants. This work demonstrates the synthesis of graphene composite with pure and Sn ion doped-ZnO and their photocatalytic properties are reported. Structural studies were carried out by X-ray diffraction and Raman spectroscopy to confirm the formation of the nanocomposites. Microstructure was characterized by scanning electron microscopy showing rod shaped ZnO and the layer structured graphene in the ZnO-graphene composite. In comparison with the undoped ZnO-graphene composite, the Sn ion doped ZnO-graphene composite have shown better degradation of methyl orange dye that is about 99% of degradation. Band gap of the composite materials was calculated to be 3.36 eV from the UV-Vis result.

Structural and photocatalytic studies on pure and Sn ion doped ZnO-graphene nanocomposites

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

Beura, Rosalin; Thangadurai, P., E-mail: thangaduraip.nst@pondiuni.edu.in

2016-05-23

Graphene based metal oxide nanocomposites have been widely used as a photocatalyst for the treatment of water pollutants. This work demonstrates the synthesis of graphene composite with pure and Sn ion doped-ZnO and their photocatalytic properties are reported. Structural studies were carried out by X-ray diffraction and Raman spectroscopy to confirm the formation of the nanocomposites. Microstructure was characterized by scanning electron microscopy showing rod shaped ZnO and the layer structured graphene in the ZnO-graphene composite. In comparison with the undoped ZnO-graphene composite, the Sn ion doped ZnO-graphene composite have shown better degradation of methyl orange dye that is aboutmore » 99% of degradation. Band gap of the composite materials was calculated to be 3.36 eV from the UV-Vis result.« less

Altitudinal patterns and controls of trace metal distribution in soils of a remote high mountain, Southwest China.

PubMed

Li, Rui; Bing, Haijian; Wu, Yanhong; Zhou, Jun; Xiang, Zhongxiang

2018-02-01

The aim of this study is to reveal the effects of regional human activity on trace metal accumulation in remote alpine ecosystems under long-distance atmospheric transport. Trace metals (Cd, Pb, and Zn) in soils of the Mt. Luoji, Southwest China, were investigated along a large altitudinal gradient [2200-3850 m above sea level (a.s.l.)] to elaborate the key factors controlling their distribution by Pb isotopic composition and statistical models. The concentrations of Cd, Pb, and Zn in the surface soils (O and A horizons) were relatively low at the altitudes of 3500-3700 m a.s.l. The enrichment factors of trace metals in the surface soils increased with altitude. After normalization for soil organic matter, the concentrations of Cd still increased with altitude, whereas those of Pb and Zn did not show a clear altitudinal trend. The effects of vegetation and cold trapping (CTE) (pollutant enrichment by decreasing temperature with increasing altitude) mainly determined the distribution of Cd and Pb in the O horizon, whereas CTE and bedrock weathering (BW) controlled that of Zn. In the A horizon, the distribution of Cd and Pb depended on the vegetation regulation, whereas that of Zn was mainly related to BW. Human activity, including ores mining and fossil fuels combustion, increased the trace metal deposition in the surface soils. The anthropogenic percentage of Cd, Pb, and Zn quantified 92.4, 67.8, and 42.9% in the O horizon, and 74.5, 33.9, and 24.9% in the A horizon, respectively. The anthropogenic metals deposited at the high altitudes of Mt. Luoji reflected the impact of long-range atmospheric transport on this remote alpine ecosystem from southern and southwestern regions.

Geologic, geochemical, and isotopic studies of a carbonate- and siliciclastic-hosted Pb-Zn deposit at Lion Hill, Vermont

USGS Publications Warehouse

Foley, Nora K.; Clark, Sandra H.B.; Woodruff, Laurel G.; Mosier, Elwin L.

1995-01-01

The prospect of an Irish-type sedimentary-exhalative origin for stratabound Pb-Zn deposits of the Paleozoic shelf of North America is of considerable importance to understanding the timing of mineralization relative to platform evolution and for evaluating the mineral resource potential of the region. Our study of the Lion Hill deposit indicates a potential for Irish-type Pb-Zn deposits in platform rocks of western Vermont; however, at Lion Hill they contain enrichments of Pb, Zn, and Cu rather than a Pb, Zn, and Ag association.

Two-step fabrication of ZnO-PVP composites with tunable visible emissions

NASA Astrophysics Data System (ADS)

Agulto, Verdad C.; Empizo, Melvin John F.; Kawano, Keisuke; Minami, Yuki; Yamanoi, Kohei; Sarukura, Nobuhiko; Yago, Allan Christopher C.; Sarmago, Roland V.

2018-02-01

We report a two-step fabrication of zinc oxide-polyvinylpyrrolidone (ZnO-PVP) composites for potential phosphor-based applications. The composites are fabricated by initially preparing ZnO microrods using hydrothermal growth method and then dip-coating the microrods into aqueous PVP solutions with varying molar concentrations. The as-prepared ZnO microrods exhibit smooth surfaces and broad visible emissions, while the ZnO-PVP composites have pitted surfaces with shifted and reduced visible emissions. These changes in the structural and optical properties, which are found to depend on the PVP concentration, are attributed to the adsorption of PVP on the microrod surface. Although the surface morphology and visible emission are modified by PVP, the composites still maintain a hexagonal wurtzite crystal structure and near-band-edge ultraviolet (UV) emission similar with the as-prepared microrods. Our results therefore suggest that the ZnO-PVP composites can be used as phosphors that offer not only properties found in both ZnO and PVP but also tunable visible emissions which can be controlled during material fabrication.

Carbon nanofibers wrapped with zinc oxide nano-flakes as promising electrode material for supercapacitors.

PubMed

Pant, Bishweshwar; Park, Mira; Ojha, Gunendra Prasad; Park, Juhyeong; Kuk, Yun-Su; Lee, Eun-Jung; Kim, Hak-Yong; Park, Soo-Jin

2018-07-15

A combination of electrospinning technique and hydrothermal process was carried out to fabricate zinc oxide nano-flakes wrapped carbon nanofibers (ZnO/CNFs) composite as an effective electrode material for supercapacitor. The morphology of the as-synthesized composite clearly revealed that the carbon nanofibers were successfully wrapped with ZnO nano-flakes. The electrochemical performance of the as-synthesized nanocomposite electrode was evaluated by the cyclic voltammetry (CV), galvanostatic charge-discharge (GDC), and electrochemical impedance spectroscopy (EIS), and compared with the pristine ZnO nanofibers. It was found that the composite exhibited a higher specific capacitance (260 F/g) as compared to pristine ZnO NFs (118 F/g) at the scan rate of 5 mV/s. Furthermore, the ZnO/CNFs composite also exhibited good capacity retention (73.33%). The obtained results indicated great potential applications of ZnO/CNFs composite in developing energy storage devices with high energy and power densities. The present work might provide a new route for utilizing ZnO based composites for energy storage applications. Copyright © 2018 Elsevier Inc. All rights reserved.

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.

Efficient radical cation stabilization of PANI-ZnO and PANI-ZnO-GO composites and its optical activity

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

Mathavan, T., E-mail: tjmathavan@gmail.com; Divya, A.; Benial, A. Milton Franklin

2016-05-23

Polyaniline (PANI) and its composites PANI-ZnO (Zinc oxide) and PANI-ZnO-GO (Graphene oxide) were successfully constructed. These materials were characterized by electron spin resonance (ESR) technique and ultraviolet visible spectrometry. The parameters such as line width, g-factor and spin concentration were deduced from ESR spectra, from the results the radical cation stabilization of PANI, PANI-ZnO and PANI-ZnO-GO composites were compared by the polaron and bipolaron formation. The absorption features obtained in the UV absorption spectra reveal the band gap of these modified PANI composites and also predicted the information of increasing and decreasing features of signal intensity and spin concentration.

Research on the Dielectric Properties of Nano-ZnO/Silicone Rubber Composites

NASA Astrophysics Data System (ADS)

Wang, Fei-feng; Yan, Dan-dan; Su, Yi; Lu, Yu-feng; Xia, Xiao-fei; Huang, Hui-min

2017-09-01

The samples of 1%, 2%, 3% and 4% Zinc Oxide (ZnO) nano-composite silicone rubber were prepared by mechanical method. The dielectric properties of each sample were measured by dielectric spectroscopy. The experimental results showed that the dielectric constant of the silicone rubber composite increases with the increase of the content of nano-ZnO. The breakdown test results showed that with the increase of the content of nano-ZnO, the breakdown strength of silicone rubber composites increased first and then decreased. The breakdown test results indicate that the nano-ZnO can reduce the breakdown strength of silicone rubber. The hydrophobic test results showed that nano-ZnO will reduce the hydrophobic of silicone rubber.

Efficient radical cation stabilization of PANI-ZnO and PANI-ZnO-GO composites and its optical activity

NASA Astrophysics Data System (ADS)

Mathavan, T.; Divya, A.; Archana, J.; Ramasubbu, A.; Benial, A. Milton Franklin; Jothirajan, M. A.

2016-05-01

Polyaniline (PANI) and its composites PANI-ZnO (Zinc oxide) and PANI-ZnO-GO (Graphene oxide) were successfully constructed. These materials were characterized by electron spin resonance (ESR) technique and ultraviolet visible spectrometry. The parameters such as line width, g-factor and spin concentration were deduced from ESR spectra, from the results the radical cation stabilization of PANI, PANI-ZnO and PANI-ZnO-GO composites were compared by the polaron and bipolaron formation. The absorption features obtained in the UV absorption spectra reveal the band gap of these modified PANI composites and also predicted the information of increasing and decreasing features of signal intensity and spin concentration.

Versatile hydrothermal synthesis of one-dimensional composite structures

NASA Astrophysics Data System (ADS)

Luo, Yonglan

2008-12-01

In this paper we report on a versatile hydrothermal approach developed to fabricate one-dimensional (1D) composite structures. Sulfur and selenium formed liquid and adsorbed onto microrods as droplets and subsequently reacted with metallic ion in solution to produce nanoparticles-decorated composite microrods. 1D composites including ZnO/CdS, ZnO/MnS, ZnO/CuS, ZnO/CdSe, and FeOOH/CdS were successfully made using this hydrothermal strategy and the growth mechanism was also discussed. This hydrothermal strategy is simple and green, and can be extended to the synthesis of various 1D composite structures. Moreover, the interaction between the shell nanoparticles and the one-dimensional nanomaterials were confirmed by photoluminescence investigation of ZnO/CdS.

Microstructure and dielectric properties of cellulose acetate-ZnO/ITO composite films based on water hyacinth

NASA Astrophysics Data System (ADS)

Diantoro, M.; Mustikasari, A. A.; Wijayanti, N.; Yogihati, C.; Taufiq, A.

2017-05-01

The electrical properties of Cellulose Acetate (CA), especially extracted from water hyacinth, is rarely informed. CA is generally more stable compared to its cellulose. It has a good potential for electronic application with specific modifications such as inducing metal oxide. A combination of intrinsic properties of Zinc Oxide (ZnO) and CA is expected as a great potential for electrical and optical applications. CA-ZnO/ITO composite film was investigated in relation with its structure, dielectric constant, and the effect of light intensity on their dielectric constant. CA-ZnO composite films were prepared with different mass of ZnO i.e. 0; 0,02; 0,04; 0,06 and 0,08 grams. CA-ZnO solution was synthesized via the mixing method with PEG:DMF solvents by using a magnetic hotplate stirrer with the rotation rate of 1500 rpm at 80°C. The CA-ZnO solution was then deposited onto ITO/glass substrate by using spin coating technique. The CA-ZnO/ITO films were annealed at 160°C to remove the remaining solvents. The effects of ZnO composition on the structure (crystallinity and morphology) and dielectric constant properties were investigated by using X-Ray Diffractometer, Scanning Electron Microscopy, Fourier Transform Infrared Spectroscopy, and LCR meter. It was shown that cellulose can be isolated from water hyacinth with the yield of 67,72 % by Chesson method and can further be transformed into CA. The X-ray diffraction pattern showed that there are 2 phases formed i.e. CA and ZnO. Furthermore, greater ZnO amount increased the crystallinity of composite films. The CA-ZnO films exhibit porous films with ZnO distributed on the CA surface films. Therefore, ZnO increases the dielectric constant of CA-ZnO composite films.

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.

Synthesis and Photocatalytic Property of ZnO/TiO2 Inverse Opals Films with Controllable Composition and Topology

NASA Astrophysics Data System (ADS)

Xu, Jiao; Yang, Bei-fang; Fu, Zheng-ping; Wen, Mei-wang; Zhao, Yong-xun

2012-04-01

A novel method to fabricate composition- and topology-controlled ZnO/TiO2 inverse opals (IO) films using a positive sacrificial ZnO IO template has been developed. This method includes a two-step process, preparation of ZnO IO by a simple electrochemical deposition using a self-assembly polystyrene colloidal crystal template and preparation of ZnO/TiO2 IO by a liquid phase deposition (LPD) process at room temperature. The composition and topology of ZnO/TiO2 IO can be easily controlled by changing the duration of the LPD. After 20 min LPD process, a ZnO/TiO2 composite IO with non-close-packed face-centered cubic air sphere array was obtained. Prolonging the duration to 60 min, a pure TiO2 IO (TIO-LPD60) with obviously thickened walls was formed. The formation mechanism for the compositional and topological variation was discussed. A preliminary study on UV photocatalytic property of the samples for degradation of methylene blue reveals that the composition and topology significantly influenced the photocatalytic activity of the IO film. The ZnO/TiO2 composite IO demonstrates a higher degree of activity than both pure ZnO and pure TiO2 IO, although they have a similar IO wall thickness. Moreover, with increasing IO wall thickness from ~52 nm to ~90 nm, TIO-LPD60 exhibits the highest level of photocatalytic performance.

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

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.

The lunar core can be a major reservoir for volatile elements S, Se, Te and Sb.

PubMed

Steenstra, Edgar S; Lin, Yanhao; Dankers, Dian; Rai, Nachiketa; Berndt, Jasper; Matveev, Sergei; van Westrenen, Wim

2017-11-06

The Moon bears a striking compositional and isotopic resemblance to the bulk silicate Earth (BSE) for many elements, but is considered highly depleted in many volatile elements compared to BSE due to high-temperature volatile loss from Moon-forming materials in the Moon-forming giant impact and/or due to evaporative loss during subsequent magmatism on the Moon. Here, we use high-pressure metal-silicate partitioning experiments to show that the observed low concentrations of volatile elements sulfur (S), selenium (Se), tellurium (Te), and antimony (Sb) in the silicate Moon can instead reflect core-mantle equilibration in a largely to fully molten Moon. When incorporating the core as a reservoir for these elements, their bulk Moon concentrations are similar to those in the present-day bulk silicate Earth. This suggests that Moon formation was not accompanied by major loss of S, Se, Te, Sb from Moon-forming materials, consistent with recent indications from lunar carbon and S isotopic compositions of primitive lunar materials. This is in marked contrast with the losses of other volatile elements (e.g., K, Zn) during the Moon-forming event. This discrepancy may be related to distinctly different cosmochemical behavior of S, Se, Te and Sb within the proto-lunar disk, which is as of yet virtually unconstrained.

Complex shaped ZnO nano- and microstructure based polymer composites: mechanically stable and environmentally friendly coatings for potential antifouling applications.

PubMed

Hölken, Iris; Hoppe, Mathias; Mishra, Yogendra K; Gorb, Stanislav N; Adelung, Rainer; Baum, Martina J

2016-03-14

Since the prohibition of tributyltin (TBT)-based antifouling paints in 2008, the development of environmentally compatible and commercially realizable alternatives is a crucial issue. Cost effective fabrication of antifouling paints with desired physical and biocompatible features is simultaneously required and recent developments in the direction of inorganic nanomaterials could play a major role. In the present work, a solvent free polymer/particle-composite coating based on two component polythiourethane (PTU) and tetrapodal shaped ZnO (t-ZnO) nano- and microstructures has been synthesized and studied with respect to mechanical, chemical and biocompatibility properties. Furthermore, antifouling tests have been carried out in artificial seawater tanks. Four different PTU/t-ZnO composites with various t-ZnO filling fractions (0 wt%, 1 wt%, 5 wt%, 10 wt%) were prepared and the corresponding tensile, hardness, and pull-off test results revealed that the composite filled with 5 wt% t-ZnO exhibits the strongest mechanical properties. Surface free energy (SFE) studies using contact angle measurements showed that the SFE value decreases with an increase in t-ZnO filler amounts. The influence of t-ZnO on the polymerization reaction was confirmed by Fourier transform infrared-spectroscopy measurements and thermogravimetric analysis. The immersion tests demonstrated that fouling behavior of the PTU/t-ZnO composite with a 1 wt% t-ZnO filler has been decreased in comparison to pure PTU. The composite with a 5 wt% t-ZnO filler showed almost no biofouling.

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.

Low-energy Coulomb excitation of neutron-rich zinc isotopes

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

Walle, J. van de; ISOLDE, CERN, Geneva; Aksouh, F.

2009-01-15

At the radioactive ion beam facility REX-ISOLDE, neutron-rich zinc isotopes were investigated using low-energy Coulomb excitation. These experiments have resulted in B(E2,2{sub 1}{sup +}{yields}0{sub 1}{sup +}) values in {sup 74-80}Zn, B(E2,4{sub 1}{sup +}{yields}2{sub 1}{sup +}) values in {sup 74,76}Zn and the determination of the energy of the first excited 2{sub 1}{sup +} states in {sup 78,80}Zn. The zinc isotopes were produced by high-energy proton- (A=74,76,80) and neutron- (A=78) induced fission of {sup 238}U, combined with selective laser ionization and mass separation. The isobaric beam was postaccelerated by the REX linear accelerator and Coulomb excitation was induced on a thin secondarymore » target, which was surrounded by the MINIBALL germanium detector array. In this work, it is shown how the selective laser ionization can be used to deal with the considerable isobaric beam contamination and how a reliable normalization of the experiment can be achieved. The results for zinc isotopes and the N=50 isotones are compared to collective model predictions and state-of-the-art large-scale shell-model calculations, including a recent empirical residual interaction constructed to describe the present experimental data up to 2004 in this region of the nuclear chart.« less

Advanced thermopower wave in novel ZnO nanostructures/fuel composite.

PubMed

Lee, Kang Yeol; Hwang, Hayoung; Choi, Wonjoon

2014-09-10

Thermopower wave is a new concept of energy conversion from chemical to thermal to electrical energy, produced from the chemical reaction in well-designed hybrid structures between nanomaterials and combustible fuels. The enhancement and optimization of energy generation is essential to make it useful for future applications. In this study, we demonstrate that simple solution-based synthesized zinc oxide (ZnO) nanostructures, such as nanorods and nanoparticles are capable of generating high output voltage from thermopower waves. In particular, an astonishing improvement in the output voltage (up to 3 V; average 2.3 V) was achieved in a ZnO nanorods-based composite film with a solid fuel (collodion, 5% nitrocellulose), which generated an exothermic chemical reaction. Detailed analyses of thermopower waves in ZnO nanorods- and cube-like nanoparticles-based hybrid composites have been reported in which nanostructures, output voltage profile, wave propagation velocities, and surface temperature have been characterized. The average combustion velocities for a ZnO nanorods/fuel and a ZnO cube-like nanoparticles/fuel composites were 40.3 and 30.0 mm/s, while the average output voltages for these composites were 2.3 and 1.73 V. The high output voltage was attributed to the amplified temperature in intermixed composite of ZnO nanostructures and fuel due to the confined diffusive heat transfer in nanostructures. Moreover, the extended interfacial areas between ZnO nanorods and fuel induced large amplification in the dynamic change of the chemical potential, and it resulted in the enhanced output voltage. The differences of reaction velocity and the output voltage between ZnO nanorods- and ZnO cube-like nanoparticles-based composites were attributed to variations in electron mobility and grain boundary, as well as thermal conductivities of ZnO nanorods and particles. Understanding this astonishing increase and the variation of the output voltage and reaction velocity, precise ZnO nanostructures, will help in formulating specific strategies for obtaining enhanced energy generation from thermopower waves.

Electrocatalytic Zinc Composites as the Efficient Counter Electrodes of Dye-Sensitized Solar Cells: Study on the Electrochemical Performances and Density Functional Theory Calculations.

PubMed

Li, Chun-Ting; Chang, Hung-Yu; Li, Yu-Yan; Huang, Yi-June; Tsai, Yu-Lin; Vittal, R; Sheng, Yu-Jane; Ho, Kuo-Chuan

2015-12-30

Highly efficient zinc compounds (Zn3N2, ZnO, ZnS, and ZnSe) have been investigated as low-cost electrocatalysts for the counter electrodes (CE) of dye-sensitized solar cells (DSSCs). Among them, Zn3N2 and ZnSe are introduced for the first time in DSSCs. The zinc compounds were separately mixed with a conducting binder, poly(3,4-ethylene-dioxythiophene):poly(styrenesulfonate) ( PSS), and thereby four composite films of Zn3N2/PEDOT:PSS, ZnO/PEDOT:PSS, ZnS/PEDOT:PSS, and ZnSe/ PSS were coated on the tin-doped indium oxide (ITO) substrates through a simple drop-coating process. In the composite film, nanoparticles of the zinc compound form active sites for the electrocatalytic reduction of triiodide ions, and PSS provides a continuous conductive matrix for fast electron transfer. By varying the weight percentage (5-20 wt %) of a zinc compound with respect to the weight of the PSS, the optimized concentration of a zinc compound was found to be 10 wt % in all four cases, based on the photovoltaic performances of the corresponding DSSCs. At this concentration (10 wt %), the composites films with Zn3N2 (Zn3N2-10), ZnO (ZnO-10), ZnS (ZnS-10), and ZnSe (ZnSe-10) rendered, for their DSSCs, power conversion efficiencies (η) of 8.73%, 7.54%, 7.40%, and 8.13%, respectively. The difference in the power conversion efficiency is explained based on the electrocatalytic abilities of those composite films as determined by cyclic voltammetry (CV), Tafel polarization plots, and electrochemical impedance spectroscopy (EIS) techniques. The energy band gaps of the zinc compounds, obtained by density functional theory (DFT) calculations, were used to explain the electrocatalytic behaviors of the compounds. Among all the zinc-based composites, the one with Zn3N2-10 showed the best electrocatalytic ability and thereby rendered for its DSSC the highest η of 8.73%, which is even higher than that of the cell with the traditional Pt CE (8.50%). Therefore, Zn3N2 can be considered as a promising inexpensive electrocatalyst to replace the rare and expensive Pt.

Morphological tuned preparation of zinc oxide: reduced graphene oxide composites for non-enzymatic fluorescence glucose sensing and enhanced photocatalysis

NASA Astrophysics Data System (ADS)

Sivalingam, Muthu Mariappan; Balasubramanian, Karthikeyan

2016-07-01

Zinc oxide: reduced graphene oxide (ZnO:rgo) composites with varying ZnO morphologies have been synthesized towards the application of non-enzymatic fluorescence (FL) glucose sensor and photocatalysis for methylene blue (MB) degradation. The phase structure of ZnO has confirmed by X-ray diffraction studies, and the band gap calculations were done by UV absorption spectra. Scanning electron microscope and Raman spectra revealed the morphological change and the vibrational studies of the prepared samples, respectively. The quenching of the FL emission band of ZnO:rgo composite sample confirmed the transfer of electrons from ZnO to rgo which inhibit the exciton recombination process. The non-enzymatic FL glucose sensing was carried out by the addition of dextrose glucose ( d-glucose) into the ZnO:rgo composite solution, which shows strong relationship between glucose concentration and the FL intensity. The photocatalytic studies showed that composite with high surface to volume ratio exhibits a maximum degradation of MB over 93 %. Our combined results ensured that the ZnO:rgo composites with varying morphologies could be an effective system for applications such as FL-based glucose sensing and photocatalytic degradation.

Improved sensitivity of polychlorinated-biphenyl-orientated porous-ZnO surface photovoltage sensors from chemisorption-formed ZnO-CuPc composites

PubMed Central

Li, Mingtao; Meng, Guowen; Huang, Qing; Zhang, Shile

2014-01-01

We report a new mechanism for the enhancement of porous-ZnO surface photovoltage (SPV) response to polychlorinated biphenyls (PCBs, a notorious class of persistent organic pollutants as global environmental hazard) based on copper phthalocyanine (CuPc) chemisorptive bonding on porous-ZnO. A new ZnO-CuPc composite is formed on the porous-ZnO surface due to the interaction between the surface ZnO and CuPc, with its valence band (VB) energy level being higher than that of the pristine porous-ZnO. So that the efficiency of the photogenerated-electron transfer from the composite VB to the adjacent ZnO's surface states is drastically increased due to the reduced energy gap between the transition states. As a result, the sensitivity of the PCB-orientated SPV sensor is much improved by showing amplified variation of the SPV-signals perturbed by PCBs adsorbed on the ZnO-CuPc@porous-ZnO sensitive material. PMID:24594662

Sonocatalytic degradation of some dyestuffs and comparison of catalytic activities of nano-sized TiO2, nano-sized ZnO and composite TiO2/ZnO powders under ultrasonic irradiation.

PubMed

Wang, Jun; Jiang, Zhe; Zhang, Liqun; Kang, Pingli; Xie, Yingpeng; Lv, Yanhui; Xu, Rui; Zhang, Xiangdong

2009-02-01

Here, a novel sonocatalyst, composite TiO2/ZnO powder, was prepared through the combination of nano-sized TiO2 and ZnO powders. Because of the appropriate adsorbability to organic pollutants and special crystal interphase between TiO2 and ZnO particles, the composite TiO2/ZnO powder exhibits a high sonocatalytic activity under ultrasonic irradiation during the degradation of acid red B. Especially, the sonocatalytic activity of composite TiO2/ZnO powder with 4:1 molar proportion treated at 500 degrees C for 50 min showed obvious improvement compared with pure nano-sized TiO2 and ZnO powders. When the experimental conditions such as 10mg/L acid red B concentration, 1.0 g/L catalyst addition amount, pH=7.0, 20 degrees C system temperature, 100 min ultrasonic time and 50 mL total volume were adopted, the satisfactory degradation ratio and rate were obtained. All experiments indicate that the sonocatalytic method using composite TiO2/ZnO powder may be a more advisable choice for the treatments of non- or low-transparent organic wastewaters in future.

Synthesis of ZnO decorated graphene nanocomposite for enhanced photocatalytic properties

NASA Astrophysics Data System (ADS)

Gayathri, S.; Jayabal, P.; Kottaisamy, M.; Ramakrishnan, V.

2014-05-01

Zinc oxide/Graphene (GZ) composites with different concentrations of ZnO were successfully synthesized through simple chemical precipitation method. The X-ray diffraction pattern and the micro-Raman spectroscopic technique revealed the formation of GZ composite, and the energy dispersive X-ray spectrometry analysis showed the purity of the prepared samples. The ZnO nanoparticles decorated graphene sheets were clearly visible in the field emission scanning electron micrograph. Raman mapping was employed to analyze the homogeneity of the prepared samples. The diffuse-reflectance spectra clearly indicated that the formation of GZ composites promoted the absorption in the visible region also. The photocatalytic activity of ZnO and GZ composites was studied by the photodegradation of Methylene blue dye. The results revealed that the GZ composites exhibited a higher photocatalytic activity than pristine ZnO. Hence, we proposed a simple wet chemical method to synthesize GZ composite and its application on photocatalysis was demonstrated.

Investigation of ZnO Nanowire Interfaces for Multi-Scale Composites

DTIC Science & Technology

2012-03-06

growth of zinc oxide ( ZnO ) nanowires on the surface of the...through the growth of zinc oxide ( ZnO ) nanowires on the surface of the reinforcing fibers. The nanowires functionally grade the interface, improve bonding...bulk composite. This has been accomplished through the growth of zinc oxide ( ZnO ) nanowires on the surface of the reinforcing fibers. ZnO

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.

Sm-Nd dating of the giant Sullivan Pb-Zn-Ag deposit, British Columbia

USGS Publications Warehouse

Jiang, Shao-Yong; Slack, John F.; Palmer, Martin R.

2000-01-01

We report here Sm and Nd isotope data for hydrothermal tourmalinites and sulfide ores from the giant Sullivan Pb-Zn-Ag deposit, which occurs in the lower part of the Mesoproterozoic Purcell (Belt) Supergroup. Whole-rock samples of quartz-tourmaline tourmalinite from the footwall alteration pipe yield a Sm-Nd isochron age of 1470 ± 59 Ma, recording synsedimentary B metasomatism of clastic sediments during early evolution of the Sullivan hydrothermal system. Data for variably altered (chloritized and/or albitized) tourmalinites from the hanging wall of the deposit, which are believed to have formed originally ca. 1470 Ma, define a younger 1076 ± 77 Ma isochron because of resetting of Sm and Nd isotopes during Grenvillian metamorphism. HCl leachates of bedded Pb-Zn ore yield a Sm-Nd isochron age of 1451 ± 46 Ma, which is consistent with syngenetic-exhalative mineralization ca. 1470 Ma; this age could also reflect a slightly younger, epigenetic hydrothermal event. Results obtained for the Sullivan deposit indicate that the Sm-Nd geochronometer has the potential to directly date mineralization and alteration in stratabound sulfide deposits that are not amenable to dating by other isotope methods.

Enhanced wound healing activity of Ag-ZnO composite NPs in Wistar Albino rats.

PubMed

Kantipudi, Sravani; Sunkara, Jhansi Rani; Rallabhandi, Muralikrishna; Thonangi, Chandi Vishala; Cholla, Raga Deepthi; Kollu, Pratap; Parvathaneni, Madhu Kiran; Pammi, Sri Venkata Narayana

2018-06-01

In the present study, silver (Ag) and Ag-zinc oxide (ZnO) composite nanoparticles (NPs) were synthesised and studied their wound-healing efficacy on rat model. Ultraviolet-visible spectroscopy of AgNPs displayed an intense surface plasmon (SP) resonance absorption at 450 nm. After the addition of aqueous Zn acetate solution, SP resonance band has shown at 413.2 nm indicating a distinct blue shift of about 37 nm. X-ray diffraction analysis Ag-ZnO composite NPs displayed existence of two mixed sets of diffraction peaks, i.e. both Ag and ZnO, whereas AgNPs exhibited face-centred cubic structures of metallic Ag. Scanning electron microscope (EM) and transmission EM analyses of Ag-ZnO composite NPs revealed the morphology to be monodispersed hexagonal and quasi-hexagonal NPs with distribution of particle size of 20-40 nm. Furthermore, the authors investigated the wound-healing properties of Ag-ZnO composite NPs in an animal model and found that rapid healing within 10 days when compared with pure AgNPs and standard drug dermazin.

Antibacterial Activity of Dental Composites Containing Zinc Oxide Nanoparticles

PubMed Central

Sevinç, Berdan Aydin; Hanley, Luke

2010-01-01

The resin-based dental composites commonly used in restorations result in more plaque accumulation than other materials. Bacterial biofilm growth contributes to secondary caries and failure of resin-based dental composites. Methods to inhibit biofilm growth on dental composites have been sought for several decades. It is demonstrated here that zinc oxide nanoparticles (ZnO-NPs) blended at 10% (w/w) fraction into dental composites display antimicrobial activity and reduce growth of bacterial biofilms by roughly 80% for a single-species model dental biofilm. Antibacterial effectiveness of ZnO-NPs was assessed against Streptococcus sobrinus ATCC 27352 grown both planktonically and as biofilms on composites. Direct contact inhibition was observed by scanning electron microscopy and confocal laser scanning microscopy while biofilm formation was quantified by viable counts. An 80% reduction in bacterial counts was observed with 10% ZnO-NP-containing composites compared with their unmodified counterpart, indicating a statistically significant suppression of biofilm growth. Although, 20% of the bacterial population survived and could form a biofilm layer again, 10% ZnO-NP-containing composites maintained at least some inhibitory activity even after the third generation of biofilm growth. Microscopy demonstrated continuous biofilm formation for unmodified composites after one day growth, but only sparsely distributed biofilms formed on 10% ZnO-NP-containing composites. The minimum inhibitory concentration of ZnO-NPs suspended in S. sobrinus planktonic culture was 50 μg/ml. 10% ZnO-NP-containing composites qualitatively showed less biofilm after one day anaerobic growth of a three-species initial colonizer biofilm after when compared to unmodified composites, but did not significantly reduce growth after three days. PMID:20225252

Effects of strain on phonon interactions and phase nucleation in several semiconductor and nano particle systems

NASA Astrophysics Data System (ADS)

Tallman, Robert E.

Raman scattering is utilized to explore the effects of applied pressure and strain on anharmonic phonon interactions and nucleation of structural transitions in several bulk and nanoparticle semiconductor systems. The systems investigated are bulk ZnS and ZnSe in several isotopic compositions, InP/CdS core/shell nanoparticles exhibiting confined and surface optical Raman modes, and amorphous selenium films undergoing photo-induced crystallization. The anharmonic decay of long-wavelength optical modes into two-phonon acoustic combinations modes is studied in 64Zn32S, 64Zn34S, natZnatS bulk crystals by measuring the TO(Gamma) Raman line-shape as a function of applied hydrostatic pressure. The experiments are carried out at room temperature and 16K for pressures up to 150 kbars using diamond-anvil cells. The most striking effects occur in 68Zn32S where the TO(Gamma) peak narrows by a factor of 10 and increases in intensity at pressures for which the TO(Gamma) frequency has been tuned into a gap in the two-phonon density of states (DOS). In all the isotopic compositions, the observed phonon decay processes can be adequately explained by a second order perturbation treatment of the anharmonic coupling between TO(Gamma) and TA + LA combinations at various critical points, combined with an adiabatic bond-charge model for the phonon DOS and the known mode Gruneisen parameters. Bulk ZnSe crystals exhibit very different behavior. Here we find that anharmonic decay alone can not explain the excessive (˜ 60 cm-1 ) broadening in the TO(Gamma) Raman peak observed as the pressure approaches to within 50kbar of the ZB -> B1 phase transition (at P ˜ 137 kbar). Rather the broadening appears to arise from antecedent nucleation of structural changes within nanoscopic domains, with the mechanism for line-shape changes being mode mixing via localization and disorder instead of anharmonicity. To sort out these contributions, pressure experiments on natural ZnSe and on isotopically pure 68Zn76Se are compared. Again we use an appropriate bond-charge model to obtain the phonon DOS. It is concluded that the antecedent nucleation mechanism is much more important in ZnSe than in ZnS. In order to further investigate interactions of vibrational modes in spatially confined systems, pressure-Raman experiments are carried out on InP/CdS core/shell nanoparticles. This system differs from most other core/shell nanoparticles systems, in that the near degeneracy of the bulk InP TO(Gamma) and CdS LO(Gamma) phonons leads to possible cross-interface mode coupling. Different confined and surface (or interface) optical modes are studied as a function of pressure up 65 kbar at 373 and 230 K. The results are compared with the predictions of dielectric continuum theory using a phenomenological macroscopic approach (PMA) to include the pressure dependence. Three different pressure media are employed, and the effects on the surface modes of their different static dielectric constants are investigated. The pressure-shifts of the observed confined and surface modes are well accounted for without the need to include cross-interface coupling. We conclude that the conventional boundary condition, of vanishing phonon amplitude at the heterointerface, remains valid in the InP/CdS nanoparticle system, in spite of the near degeneracy of the bulk optical phonons. Photo-induced crystallization in amorphous selenium (a-Se) was also explored in this dissertation, as another example of a nanoscopic nucleation process influenced by strain, in this case internal strain. In order to observe photo-crystallization, the Raman spectra of commercial a-Se films used as targets in high-gain avalanche rushing photodetectors (HARP) cameras was studied at temperatures in the range 260 - 330 K. We find a rich temperature behavior that reflects the competition of changes in viscosity and strain, and defines four distinct regimes. These results are in qualitative accord with a theory by R.B.Stephens treating the effects of local strain on the secondary growth of crystalline nuclei in a-Se. We were able to conclude that the growth of trigonal selenium is driven by local strain, and that the relaxation of this strain field around the glass transition temperature suppresses crystalline growth until thermally assisted processes accelerate the photo-crystallization at higher temperatures. The observed nucleation kinetics was also found to be relevant to understanding the formation of blemishes in the output images of advanced HARP video cameras.

The effect of annealing on structural, optical and electrical properties of ZnS/porous silicon composites

NASA Astrophysics Data System (ADS)

Wang, Cai-Feng; Li, Qing-Shan; Hu, Bo; Li, Wei-Bing

2009-06-01

ZnS films were prepared by pulsed laser deposition (PLD) on porous silicon (PS) substrates. This paper investigates the effect of annealing temperature on the structural, morphological, optical and electrical properties of ZnS/PS composites by x-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence (PL) and I-V characteristics. It is found that the ZnS films deposited on PS substrates were grown in preferred orientation along β-ZnS (111) direction, and the intensity of diffraction peak increases with increasing annealing temperature, which is attributed to the grain growth and the enhancement of crystallinity of ZnS films. The smooth and uniform surface of the as-prepared ZnS/PS composite becomes rougher through annealing treatment, which is related to grain growth at the higher annealing temperature. With the increase of annealing temperature, the intensity of self-activated luminescence of ZnS increases, while the luminescence intensity of PS decreases, and a new green emission located around 550 nm appeared in the PL spectra of ZnS/PS composites which is ascribed to the defect-center luminescence of ZnS. The I-V characteristics of ZnS/PS heterojunctions exhibited rectifying behavior, and the forward current increases with increasing annealing temperature.

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.

Synthesis of CdS/ZnO/graphene composite with high-efficiency photoelectrochemical activities under solar radiation

NASA Astrophysics Data System (ADS)

Han, Weijia; Ren, Long; Qi, Xiang; Liu, Yundan; Wei, Xiaolin; Huang, Zongyu; Zhong, Jianxin

2014-04-01

A novel ternary CdS/ZnO/graphene composite has been successfully prepared by loading ZnO and CdS nanoparticles in graphene nanosheets via a facile one-step hydrothermal method. The microstructures and properties have been examined by X-ray diffraction (XRD), scanning electron microscopy with an energy dispersive spectroscope (EDS), transmission electron microscopy, Raman and UV-vis diffuse reflectance spectra (DRS). The characterization results reveal that the crystalline of the composite is very well, the graphene sheets were tightly coated with ZnO and CdS nanoparticles, and the light-harvesting was effectively strengthened. Taking photoelectrochemical test, the ternary CdS/ZnO/graphene composite exhibits enhanced photocatalytic activity compared with its foundation matrix binary composites and pure ZnO and CdS. The improved photocatalytic performance can be attributed to the enhanced light absorption, the extremely efficient charge separation, as well as superior durability of the ternary composite. It is proposed that graphene-based composites by coupling graphene to suitable, multiple semiconductors can not only greatly improve the capacity for photocatalytic, but also expand the exploration and utilization of graphene-based nanocomposites for energy conversion.

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.

Hydrothermal zebra dolomite in the Great Basin, Nevada--attributes and relation to Paleozoic stratigraphy, tectonics, and ore deposits

USGS Publications Warehouse

Diehl, S.F.; Hofstra, A.H.; Koenig, A.E.; Emsbo, P.; Christiansen, W.; Johnson, Chad

2010-01-01

In other parts of the world, previous workers have shown that sparry dolomite in carbonate rocks may be produced by the generation and movement of hot basinal brines in response to arid paleoclimates and tectonism, and that some of these brines served as the transport medium for metals fixed in Mississippi Valley-type (MVT) and sedimentary exhalative (Sedex) deposits of Zn, Pb, Ag, Au, or barite. Numerous occurrences of hydrothermal zebra dolomite (HZD), comprised of alternating layers of dark replacement and light void-filling sparry or saddle dolomite, are present in Paleozoic platform and slope carbonate rocks on the eastern side of the Great Basin physiographic province. Locally, it is associated with mineral deposits of barite, Ag-Pb-Zn, and Au. In this paper the spatial distribution of HZD occurrences, their stratigraphic position, morphological characteristics, textures and zoning, and chemical and stable isotopic compositions were determined to improve understanding of their age, origin, and relation to dolostone, ore deposits, and the tectonic evolution of the Great Basin. In northern and central Nevada, HZD is coeval and cogenetic with Late Devonian and Early Mississippian Sedex Au, Zn, and barite deposits and may be related to Late Ordovician Sedex barite deposits. In southern Nevada and southwest California, it is cogenetic with small MVT Ag-Pb-Zn deposits in rocks as young as Early Mississippian. Over Paleozoic time, the Great Basin was at equatorial paleolatitudes with episodes of arid paleoclimates. Several occurrences of HZD are crosscut by Mesozoic or Cenozoic intrusions, and some host younger pluton-related polymetallic replacement and Carlin-type gold deposits. The distribution of HZD in space (carbonate platform, margin, and slope) and stratigraphy (Late Neoproterozoic Ediacaran-Mississippian) roughly parallels that of dolostone and both are prevalent in Devonian strata. Stratabound HZD is best developed in Ediacaran and Cambrian units, whereas discordant HZD is proximal to high-angle structures at the carbonate platform margin, such as strike-slip and growth faults and dilational jogs. Fabric-selective replacement and dissolution features (e.g., collapse breccias, voids with geopetal textures) are common, with remaining void space lined with light-colored dolomite crystals that exhibit zoning under cathodoluminescence. Zoned crystals usually contain tiny ( ~70 degrees C. The oxygen isotopic compositions of HZD are consistent with formation temperatures of 50-150 degrees C requiring brine circulation to depths of 2-5 km, or more. The few HZD occurrences with the highest concentrations of metals (especially Fe, Mn, and Zn) and the largest isotopic shifts are closely associated with Sedex or MVT deposits known to have formed from hotter brines (e.g., Th > 150-250 degrees C). These relationships permit that HZD formed at about the same time as dolostone, from brines produced by the evaporation of seawater during arid paleoclimates at equatorial paleolatitudes. Both dolostone and HZD may have formed as basinal brines, which migrated seaward from evaporative pans on the platform, with dolostone forming at low temperatures along shallow migration pathways through permeable limestones, and HZD forming at high temperatures along deeper migration pathways through basal aquifers and dilatant high-angle faults. The small MVT deposits were chemical traps where hot brines encountered rocks or fluids containing reduced sulfur. The abundant Sedex deposits mark sites where hot brine discharged at the seafloor in adjacent basins. Thus the distribution of HZD may map deep migration pathways and upflow zones between eastern shallow marine facies, where evaporative brine could have been generated, and western Sedex deposits, where heated brines discharged along faults into platform margin, slope, and basin facies. The small size and scarcity of Pb-Zn depos

SiO2/ZnO Composite Hollow Sub-Micron Fibers: Fabrication from Facile Single Capillary Electrospinning and Their Photoluminescence Properties.

PubMed

Song, Guanying; Li, Zhenjiang; Li, Kaihua; Zhang, Lina; Meng, Alan

2017-02-24

In this work, SiO2/ZnO composite hollow sub-micron fibers were fabricated by a facile single capillary electrospinning technique followed by calcination, using tetraethyl orthosilicate (TEOS), polyvinylpyrrolidone (PVP) and ZnO nanoparticles as raw materials. The characterization results of the scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) spectra indicated that the asprepared composite hollow fibers consisted of amorphous SiO2 and hexagonal wurtzite ZnO. The products revealed uniform tubular structure with outer diameters of 400-500 nm and wall thickness of 50-60 nm. The gases generated and the directional escaped mechanism was proposed to illustrate the formation of SiO2/ZnO composite hollow sub-micron fibers. Furthermore, a broad blue emission band was observed in the photoluminescence (PL) of SiO2/ZnO composite hollow sub-micron fibers, exhibiting great potential applications as blue light-emitting candidate materials.

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.

Ag nanoparticle-functionalized ZnO micro-flowers for enhanced photodegradation of herbicide derivatives

NASA Astrophysics Data System (ADS)

Xu, Yan; Wu, Shumin; Li, Xianliang; Meng, Hao; Zhang, Xia; Wang, Zhuopeng; Han, Yide

2017-07-01

We demonstrate a general strategy to design step by step the Ag nanoparticle-functionalized ZnO micro-flowers (Ag/ZnO composites). XRD patterns confirmed the presence of Ag nanoparticles in ZnO/Ag composites, and the SEM and TEM results further demonstrated that Ag nanoparticles were highly dispersed and anchored onto the surface of each ZnO nanosheets. By using the ZnO/Ag composites, the photodegradation of two herbicide derivatives, metamitron and metribuzin, were studied. The enhanced photocatalytic performance was ascribed to the fact that the Ag deposition could reduce the recombination probability of electron-hole pairs, and the photocatalytic mechanism were also investigated in this paper.

Cosputtering crystal growth of zinc oxide-based composite films: From the effects of doping to phase on photoactivity and gas sensing properties

NASA Astrophysics Data System (ADS)

Liang, Yuan-Chang; Lee, Chia-Min

2016-10-01

ZnO-In2O3 (InO) composite thin films were grown by radio frequency cosputtering ZnO and InO ceramic targets in this study. The indium content of the composite films was varied from 1.7 at. % to 8.2 at. % by varying the InO sputtering power during cosputtering thin-film growth. X-ray diffraction and transmission electron microscopy analysis results show that the high indium content leads to the formation of a separated InO phase in the ZnO matrix. The surface crystallite size and roughness of the ZnO-InO composite films grown here increased with an increasing indium content. Furthermore, under the conditions of a higher indium content and InO sputtering power, the number of crystal defects in the composite films increased, and the optical absorbance edge of the composite films broadened. The photoactivity and ethanol gas sensing response of the ZnO-InO composite films increased as their indium content increased; this finding is highly correlated with the microstructural evolution of ZnO-InO composite films of various indium contents, which is achieved by varying the InO sputtering power during cosputtering.

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.

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

Highly selective room temperature NO2 gas sensor based on rGO-ZnO composite

NASA Astrophysics Data System (ADS)

Jyoti, Kanaujiya, Neha; Varma, G. D.

2018-05-01

Blending metal oxide nanoparticles with graphene or its derivatives can greatly enhance gas sensing characteristics. In the present work, ZnO nanoparticles have been synthesized via reflux method. Thin films of reduced graphene oxide (rGO) and composite of rGO-ZnO have been fabricated by drop casting method for gas sensing application. The samples have been characterized by X-ray diffraction (XRD) and Field-emission scanning electron microscope (FESEM) for the structural and morphological studies respectively. Sensing measurements have been carried out for the composite film of rGO-ZnO for different concentrations of NO2 ranging from 4 to 100 ppm. Effect of increasing temperature on the sensing performance has also been studied and the rGO-ZnO composite sensor shows maximum percentage response at room temperature. The limit of detection (LOD) for rGO-ZnO composite sensor is 4ppm and it exhibits a high response of 48.4% for 40 ppm NO2 at room temperature. To check the selectivity of the composite sensor, sensor film has been exposed to 40 ppm different gases like CO, NH3, H2S and Cl2 at room temperature and the sensor respond negligibly to these gases. The present work suggests that rGO-ZnO composite material can be a better candidate for fabrication of highly selective room temperature NO2 gas sensor.

Ore genesis of the Wusihe carbonate-hosted Zn-Pb deposit in the Dadu River Valley district, Yangtze Block, SW China: evidence from ore geology, S-Pb isotopes, and sphalerite Rb-Sr dating

NASA Astrophysics Data System (ADS)

Xiong, Suo-Fei; Gong, Yong-Jun; Jiang, Shao-Yong; Zhang, Xiao-Jing; Li, Qian; Zeng, Guo-Ping

2018-01-01

The Wusihe carbonate-hosted Zn-Pb deposit (3.7 Mt. Zn + Pb at a grade of 8.6% Zn and 2.0% Pb) is the largest deposit in the Dadu River Valley district of the Sichuan-Yunnan-Guizhou metallogenic province of southwest China. Three types of orebodies occur: (1) stratiform, banded and lamellar, within dolomite of the Neoproterozoic Dengying Formation; (2) vein type; and (3) breccia type. Four stages of mineralization are distinguished: (i) pyrite stage, (ii) pyrite-pyrrhotite-galena-sphalerite-bitumen stage, (iii) sphalerite-galena stage, and (iv) bitumen-calcite stage. Sphalerite and galena from stages II and III show δ34S ranges from +7.1 to +9.7‰ and +9.1 to +13.1‰, respectively. High-precision in situ lead isotope analyses of sulfides show 208Pb/204Pb, 207Pb/204Pb, and 206Pb/204Pb ratios of 37.938 to 38.336, 15.579 to 15.682, and 17.951 to 18.195, respectively, which suggest a mixing of lead from the basement and the host rocks. Rb-Sr isotope analyses for six sphalerite samples of stage II yielded an isochron age of 411 ± 10 Ma (MSWD = 1.4). Combining all available ore geology and geochemical data, together with fluid inclusion data reported previously, we suggest that the Wusihe deposit is a Mississippi Valley-type (MVT) deposit.

Improvement of the mechanical properties and corrosion resistance of biodegradable β-Ca3(PO4)2/Mg-Zn composites prepared by powder metallurgy: the adding β-Ca3(PO4)2, hot extrusion and aging treatment.

PubMed

Yan, Yang; Kang, Yijun; Li, Ding; Yu, Kun; Xiao, Tao; Deng, Youwen; Dai, Han; Dai, Yilong; Xiong, Hanqing; Fang, Hongjie

2017-05-01

In this study, 10%β-Ca 3 (PO 4 ) 2 /Mg-6%Zn (wt.%) composites with Mg-6%Zn alloy as control were prepared by powder metallurgy. After hot extrusion, the as-extruded composites were aged for 72h at 150°C. The effects of the adding β-Ca 3 (PO 4 ) 2 , hot extrusion and aging treatment on their microstructure, mechanical properties and corrosion resistance were investigated. The XRD results identified α-Mg, MgZn phase and β-Ca 3 (PO 4 ) 2 phase in these composites. After hot extrusion, grains were significantly refined, and the larger-sized β-Ca 3 (PO 4 ) 2 particles and coarse MgZn phases were broken into linear-distributed β-Ca 3 (PO 4 ) 2 and MgZn phases along the extrusion direction. After aging treatment, the elements of Zn, Ca, P and O presented a more homogeneous distribution. The compressive strengths of the β-Ca 3 (PO 4 ) 2 /Mg-Zn composites were approximately double those of natural bone, and their densities and elastic moduli matched those of natural bone. The immersion tests and electrochemical tests revealed that the adding β-Ca 3 (PO 4 ) 2 , hot extrusion and aging treatment could promote the formation of protective corrosion product layer on the sample surface in Ringer's solution, which improved corrosion resistance of the β-Ca 3 (PO 4 ) 2 /Mg-Zn composites. The XRD results indicated that the corrosion product layer contained Mg(OH) 2 , β-Ca 3 (PO 4 ) 2 and hydroxyapatite (HA). The cytotoxicity assessments showed the as-extruded β-Ca 3 (PO 4 ) 2 /Mg-Zn composite aged for 72h was harmless to L-929 cells. These results suggested that the β-Ca 3 (PO 4 ) 2 /Mg-Zn composites prepared by powder metallurgy were promising to be used for bone tissue engineering. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Fenton-like oxidation of 4-chlorophenol using H2O2 in situ generated by Zn-Fe-CNTs composite.

PubMed

Liu, Yong; Fan, Qing; Liu, Yanlan; Wang, Jianlong

2018-05-15

In this paper, a zinc-iron-carbon nanotubes (Zn-Fe-CNTs) composite was prepared, characterized and used to develop a Fenton-like system of Zn-Fe-CNTs/O 2 for the degradation of 4-chlorophenol (4-CP), in which H 2 O 2 was generated in situ from zinc-carbon galvanic cells and oxygen in aqueous solution was activated by iron attached on the surface of CNTs to produce ·OH radicals for the oxidation of 4-CP. The experimental results showed that the particles of Zn and Fe in Zn-Fe-CNTs composite were adhered to the surface of CNTs, which accelerated the electron transfer process. The BET area of Zn-Fe-CNTs composite was 32.9 m 2 /g. The contents of Zn and Fe (% w) in the composite were 44.7% and 4.2%, respectively. The removal efficiency of 4-CP and TOC in Zn-Fe-CNTs/O 2 system was 90.8% and 52.9%, respectively, with the initial pH of 2.0, O 2 flow rate of 800 mL/min, Zn-Fe-CNTs dosage of 1.0 g/L, 4-CP concentration of 50 mg/L and reaction time of 20 min. Based on the analysis of the degradation intermediate products with LC-MS and IC, a possible degradation pathway of 4-CP in Zn-Fe-CNTs/O 2 system was proposed. Copyright © 2018 Elsevier Ltd. All rights reserved.

Enhanced photoluminescence property and broad color emission of ZnGa2O4 phosphor due to the synergistic role of Eu3+ and carbon dots

NASA Astrophysics Data System (ADS)

Huo, Qiuyue; Tu, Weixia; Guo, Lin

2017-10-01

ZnGa2O4 phosphors co-composited with nanoscale carbon dots (CDs) and Eu3+ were presented for the tunable color emission. Novel single phase CDs or/and Eu3+ composited ZnGa2O4 phosphors were synthesized by microwave hydrothermal method and their optical properties were investigated. The ZnGa2O4 phosphors composited with CDs exhibited an intense broad blue light emission at 421 nm and a more enhanced photoluminescence intensity than those without CDs. The Eu3+ composited ZnGa2O4 phosphors gave an ideal red color emission. The CDs/Eu3+ co-composited ZnGa2O4 phosphors exhibited a wide emission band peak at 450 nm and narrow emission peak at 618 nm. Furthermore, the tunable color emissions of CDs/Eu3+ co-composited ZnGa2O4 phosphors from blue to the white light region, and then to red were obtained with the increasing Eu3+ concentration, which can be a promising single phased phosphor candidate in light emitting diodes. Broadly tunable emission single phased phosphor is tuned firstly through the synergistic role of the non-metal element and the rare earth metal ions.

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.

Synthesis of magnetic Bi2O2CO3/ZnFe2O4 composite with improved photocatalytic activity and easy recyclability

NASA Astrophysics Data System (ADS)

Liu, Yumin; Ren, Hao; Lv, Hua; Guang, Jing; Cao, Yafei

2018-03-01

Magnetic Bi2O2CO3/ZnFe2O4 heterojunction photocatalysts with varying content of ZnFe2O4 were constructed by modifying Bi2O2CO3 nanosheets with mesoporous ZnFe2O4 nanoparticles. The photoactivity of the products was investigated by decomposing RhodamineB (RhB) and it was found that the photoactivity of Bi2O2CO3/ZnFe2O4 composite was closely related to the loading amount of ZnFe2O4. Under simulant sunlight irradiation, the optimum photoactivity of Bi2O2CO3/ZnFe2O4 composite was almost 2.3 and 2.1 times higher than that by bare ZnFe2O4 and Bi2O2CO3, respectively. The improved photoactivity resulted from the synergistic effect of Bi2O2CO3 and ZnFe2O4, which not only extended the photoabsorption region but also significantly facilitated the interfacial charge transfer. Besides the high photocatalytic performance, Bi2O2CO3/ZnFe2O4 composite also exhibited excellent stable and recycling properties, which enabled it have great potential in a long-term practical use.

Seaching for a Silver Lining: Using Pb Isotopes to Constrain the Source of Argentiferous Galena at La Isabela

NASA Astrophysics Data System (ADS)

Thibodeau, A. M.; Killick, D. J.; Ruiz, J.; Chesley, J. T.; Baker, M.

2005-12-01

This study investigates the smelting and refining of argentiferous galena at La Isabela, Dominican Republic (1493-1498), the town founded by Columbus on his second voyage to the Americas. Archaeologists recovered approximately 100 kilograms of galena and 200 kilograms of metallurgical slag near the remains of a crude furnace unearthed at the site (Deagan and Cruxent 2002). The purpose of this study was to determine if these remains are evidence that members of Columbus's fleet prospected for silver during his second expedition. Samples of ore and slag were examined as metallographic polished sections, and petrographic thin sections by optical and scanning electron microscopes. The composition of the ore and slag allows us to infer these ores were processed in a two-stage procedure to produce silver metal and a lead silicate slag. Electron microprobe analysis of galena indicates highly variable but low Ag content (50 ppm), which may account for the fact some of the ore was left unprocessed. Lead isotope analysis by multi-collector ICP-MS indicates that the galena likely came from a single source and was not mined within the Caribbean. Instead, the isotopic signature of these ores is consistent with an Old World source, possibly in the Linares-La Carolina Pb-Zn vein field of southwestern Spain.

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 ...

Controlled synthesis and microwave absorption properties of Ni0.6Zn0.4Fe2O4/PANI composite via an in-situ polymerization process

NASA Astrophysics Data System (ADS)

Wang, Min; Ji, Guangbin; Zhang, Baoshan; Tang, Dongming; Yang, Yi; Du, Youwei

2015-03-01

The binary composites of conducting polyaniline (PANI) and nickle zinc ferrite were synthesized by an in-situ polymerization process, and the electromagnetic absorption properties of the composites were also investigated. The FT-IR spectra present the peaks of PANI (1562, 1481, 1301, 1109, and 799 cm-1) and the bonds of NiZn ferrite (579 and 390 cm-1), indicating the existence of both NiZn ferrite particles and PANI in the composites. With the increasing ratio of nickle zinc ferrite, the composites distributes in irregular compared with pure PANI and Ni0.6Zn0.4Fe2O4. The TG curves of the pure PANI and PANI/Ni0.6Zn0.4Fe2O4 composites with different molar ratios clearly show the increase percentage of the ferrite in the composites. Furthermore, we found that the excellent electromagnetic absorption properties and wide absorption bandwidth can be achieved by adjusting proper molar ratios Ni0.6Zn0.4Fe2O4 to PANI. The maximum reflection loss of Ni0.6Zn0.4Fe2O4/PANI can reach to -41 dB at 12.8 GHz and the bandwidth exceeding -10 dB can reach to 5 GHz with the absorber thickness of 2.6 mm at the molar ratio of 1:2. This can be attributed to the enhancing magnetic loss and the better impedance matching. Therefore, Ni0.6Zn0.4Fe2O4/PANI ferrite composites can become a new kind of candidate in the field of the microwave absorbing.

The quadrupole moments of Cd and Zn isotopes - an apology

NASA Astrophysics Data System (ADS)

Haas, H.; Barbosa, M. B.; Correia, J. G.

2016-12-01

In 2010 we presented an update of the nuclear quadrupole moments (Q) for the Cd and Zn isotopes, based essentially on straightforward density functional (DF) calculations (H. Haas and J.G. Correia, Hyperfine Interact 198, 133-137 (2010)). It has been apparent for some years that the standard DF procedure obviously fails, however, to reproduce the known electric-field gradient (EFG) for various systems, typical cases being Cu2O, As and Sb, and the solid halogens. Recently a cure for this deficiency has been found in the hybrid DF technique. This method is now applied to solid Cd and Zn, and the resultant quadrupole moments are about 15 % smaller than in our earlier report. Also nuclear systematics, using the recently revised values of Q for the long-lived 11/2 isomers in111Cd to129Cd, together with earlier PAD data for107,109Cd, leads to the same conclusion. In addition, EFG calculations for the cadmium dimethyl molecule further support the new values: Q(111Cd, 5/2+) = .683(20) b, Q(67Zn, gs) = .132(5) b. This implies, that the value for the atomic EFG in the 3it {P}1 state of Zn must be revised, as it has been for Cd.

A new, simple and precise method for measuring cyclotron proton beam energies using the activity vs. depth profile of zinc-65 in a thick target of stacked copper foils.

PubMed

Asad, A H; Chan, S; Cryer, D; Burrage, J W; Siddiqui, S A; Price, R I

2015-11-01

The proton beam energy of an isochronous 18MeV cyclotron was determined using a novel version of the stacked copper-foils technique. This simple method used stacked foils of natural copper forming 'thick' targets to produce Zn radioisotopes by the well-documented (p,x) monitor-reactions. Primary beam energy was calculated using the (65)Zn activity vs. depth profile in the target, with the results obtained using (62)Zn and (63)Zn (as comparators) in close agreement. Results from separate measurements using foil thicknesses of 100, 75, 50 or 25µm to form the stacks also concurred closely. Energy was determined by iterative least-squares comparison of the normalized measured activity profile in a target-stack with the equivalent calculated normalized profile, using 'energy' as the regression variable. The technique exploits the uniqueness of the shape of the activity vs. depth profile of the monitor isotope in the target stack for a specified incident energy. The energy using (65)Zn activity profiles and 50-μm foils alone was 18.03±0.02 [SD] MeV (95%CI=17.98-18.08), and 18.06±0.12MeV (95%CI=18.02-18.10; NS) when combining results from all isotopes and foil thicknesses. When the beam energy was re-measured using (65)Zn and 50-μm foils only, following a major upgrade of the ion sources and nonmagnetic beam controls the results were 18.11±0.05MeV (95%CI=18.00-18.23; NS compared with 'before'). Since measurement of only one Zn monitor isotope is required to determine the normalized activity profile this indirect yet precise technique does not require a direct beam-current measurement or a gamma-spectroscopy efficiency calibrated with standard sources, though a characteristic photopeak must be identified. It has some advantages over published methods using the ratio of cross sections of monitor reactions, including the ability to determine energies across a broader range and without need for customized beam degraders. Copyright © 2015 Elsevier Ltd. All rights reserved.

Ni-P/Zn-Ni compositionally modulated multilayer coatings - Part 1: Electrodeposition and growth mechanism, composition, morphology, roughness and structure

NASA Astrophysics Data System (ADS)

Bahadormanesh, Behrouz; Ghorbani, Mohammad

2018-06-01

The Ni-P/Zn-Ni compositionally modulated multilayer coatings CMMCs were electrodeposited from a single bath by switching the cathodic current density. The composition, surface morphology, roughness, layers growth pattern as well as the phase structure of deposits were extensively studied via SEM, EDS, AFM and XRD analysis. Effects of bath ingredients on the electrodeposition behavior were analyzed through cathodic linear sweep voltammetry. Although the concentration of Zn2+ in bath was 13 times higher than Ni2+, the Zn-Ni deposition potential was much nearer to Ni deposition potential rather than that of Zn. Addition of NaH2PO2 to the Ni deposition bath considerably raised the current density and shifted the crystallization potential of Ni to more nobble values. Codeposition of P with Zn-Ni alloy lead to crack formation in the monolayer that was deposited in 60 mA/cm2. However, the cracks were not observed in the Zn-Ni layers of multilayers. Zn-Ni layers in CMMCs exhibited a three-dimensional pattern of growth while that of Ni-P layers was two-dimensional. Also, the Ni-P deposits tends to fill the discontinuities in Zn-Ni layers and performed leveling properties and lowered the surface roughness of Zn-Ni layers and CMMCs. Structural analysis demonstrated that Ni-P layers were amorphous and the Zn-Ni layers exhibited crystallite phase of Zn11Ni2. Thus, the Ni-P/Zn-Ni CMMCs comprised of alternate layers of amorphous Ni-P and nanocrystalline Zn Ni.

Facile synthesis of zinc oxide nanoparticles decorated graphene oxide composite via simple solvothermal route and their photocatalytic activity on methylene blue degradation.

PubMed

Atchudan, Raji; Edison, Thomas Nesakumar Jebakumar Immanuel; Perumal, Suguna; Karthikeyan, Dhanapalan; Lee, Yong Rok

2016-09-01

Zinc oxide nanoparticles decorated graphene oxide (ZnO@GO) composite was synthesized by simple solvothermal method where zinc oxide (ZnO) nanoparticles and graphene oxide (GO) were synthesized via simple thermal oxidation and Hummers method, respectively. The obtained materials were thoroughly characterized by various physico-chemical techniques such as X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Raman spectrum shows the intensity of D to G value was close to one which confirms the obtained GO and ZnO@GO composite possesses moderate graphitization. TEM images shows the ZnO nanoparticles mean size of 15±5nm were dispersed over the wrinkled graphene layers. The photocatalytic performance of ZnO@GO composite on degradation of methylene blue (MB) is investigated and the results show that the GO plays an important role in the enhancement of photocatalytic performance. The synthesized ZnO@GO composite achieves a maximum degradation efficiency of 98.5% in a neutral solution under UV-light irradiation for 15min as compared with pure ZnO (degradation efficiency is 49% after 60min of irradiation) due to the increased light absorption, the reduced charge recombination with the introduction of GO. Moreover, the resulting ZnO@GO composite possesses excellent degradation efficiency as compared to ZnO nanoparticles alone on MB. Copyright © 2016 Elsevier B.V. All rights reserved.

Reduced graphene Oxide/ZnO nanostructures based rectifier diode

NASA Astrophysics Data System (ADS)

Bhatnagar, Sameeksha; Kumar, Ravi; Sharma, Monika; Kuanr, Bijoy K.

2017-05-01

We report on the fabrication and characterization of graphene oxide and reduced graphene oxide/ZnO nanostructures on ITO-coated glass substrates for the rectification properties of a heterojunction device. The composites of GO/ZnO and rGO/ZnO were synthesized by the modified Hummers method followed by annealing process in N2 and H2 ambient atmosphere at various temperatures. The structural and compositional analysis of the composite material have been investigated using X-ray diffraction spectroscopy and Raman spectroscopy. The optical properties of the composite films were studied by UV-visible spectroscopy and the band-gap was obtained by Tauc's plot. The band-gap reduces to 2.4 eV for the composite film as compared to ZnO film 3.26 eV. The I-V characteristics of ZnO thin films and rGO/ZnO films were done for different light conditions viz dark, ambient light and UV-illumination. It has been observed that the threshold voltage decreases when the sample was placed in UV-illumination. A direct variation in photo-response is revealed with the bias voltage as well as UV illumination. The fabricated device could be used as an Ultraviolet Photo-detector.

Self-sensitization of tetracycline degradation with simulated solar light catalyzed by ZnO@montmorillonite

NASA Astrophysics Data System (ADS)

Zyoud, Ahed; Jondi, Waheed; AlDaqqah, Najat; Asaad, Sara; Qamhieh, Naser; Hajamohideen, AbdulRazack; Helal, Muath H. S.; Kwon, Hansang; Hilal, Hikmat S.

2017-12-01

Zinc oxide (ZnO) nano-particles were chemically deposited onto montmorillonite (MONT) clay particles. The composite ZnO@MONT was then characterized and used as a catalyst for photo-degradation of aqueous tetracycline. Unlike earlier studies, solar simulated light can be effectively used in this work. The composite shows high efficiency as adsorbent and as a photo-degradation catalyst. Both adsorbed and dissolved tetracycline molecules undergo mineralization under the photo-catalytic conditions, and up to 94% of the contaminant gross amount is completely mineralized. Other forms of ZnO particles, commercial ZnO and synthetic ZnO particles were examined in separate experiments. The ZnO@MONT is superior to both pristine counterparts. The ability of tetracycline to sensitize the supported ZnO particles, to solar simulated light, before being photo-degraded itself, is discussed here for the first time. In addition to enhanced catalytic activity of the ZnO@MONT, the composite can be efficiently recovered and reused with no significant loss of efficiency.

Aloe vera mediated hydrothermal synthesis of reduced graphene oxide decorated ZnO nanocomposite: Luminescence and antioxidant properties

NASA Astrophysics Data System (ADS)

Kavyashree, D.; Nagabhushana, H.; Ananda Kumari, R.; Basavaraj, R. B.; Suresh, D.; Daruka Prasad, B.; Sharma, S. C.

2016-05-01

A zinc oxide/reduced graphene oxide (ZnO/rGO) nanocomposite was fabricated by facile hydrothermal route using Aloe vera gel as surfactant. The PL emission spectrum of the ZnO/rGO composite consists of four peaks at around 380, 394, 449 and 465nm. The PL intensity is found to diminish in ZnO-rGO composites rather than in pure ZnO, which was attributed to electron transfer from ZnO to rGO. A single intense glow curve was recorded in rGo-ZnO for a dose range of 1-8kGy. The TL response curve of rGO-ZnO is found to be a simple glow curve structure, linear dependence over a dose range of 1-8kGy. The obtained ZnO/rGO composite could provide a facile and eco-friendly method for the development of graphene-based nanocomposites with promising applications in radiation dosimetry and antioxidant activities.

Composition Dependence of the Hydrostatic Pressure Coefficients of the Bandgap of ZnSe(1-x)Te(x) Alloys

NASA Technical Reports Server (NTRS)

Wu, J.; Yu, K. M.; Walukiewicz, W.; Shan, W.; Ager, J. W., III; Haller, E. E.; Miotkowski, I.; Ramdas, A. K.; Su, Ching-Hua

2003-01-01

Optical absorption experiments have been performed using diamond anvil cells to measure the hydrostatic pressure dependence of the fundamental bandgap of ZnSe(sub 1-xTe(sub x) alloys over the entire composition range. The first and second-order pressure coefficients are obtained as a function of composition. Starting from the ZnSe side, the magnitude of both coefficients increases slowly until x approx. 0.7, where the ambient-pressure bandgap reaches a minimum. For larger values of x the coefficients rapidly approach the values of ZnTe. The large deviations of the pressure coefficients from the linear interpolation between ZnSe and ZnTe are explained in terms of the band anticrossing model.

Synthesis and characterization of Graphene oxide/Zinc oxide nanorods sandwich structure

NASA Astrophysics Data System (ADS)

Boukhoubza, I.; Khenfouch, M.; Achehboune, M.; Mouthudi, B.; Zorkani, I.; Jorio, A.

2018-03-01

Graphene-ZnO nanostructures composite materials have been used as very efficient candidates for various optoelectronic applications. Nowadays, the composite structure formation of ZnO nanostructures with graphene or graphene oxide is a novel, cost effective and efficient approach to control the morphology, surface defect states, band gap of ZnO nanocrystals. In this paper, we have prepared ZnO nanorods between two layers graphene oxide (GO/ZnO NRs/GO) via a simple hydrothermal method. Their morphology, structural and optical properties have been investigated. The obtained results of our composites GO/ZnO NRs/GO presented here showing an enhancement in the structural and optical properties. Thus may hold great promise to the development of the optoelectronic devices.

Evidencing lead deposition at the urban scale using "short-lived" isotopic signatures of the source term (Pb-Zn refinery)

NASA Astrophysics Data System (ADS)

Franssens, Matthias; Flament, Pascal; Deboudt, Karine; Weis, Dominique; Perdrix, Espéranza

2004-09-01

To demonstrate the ability of the lead isotope signature technique to evidence the spatial extent of an industrial Pb deposition plume at a local scale, dry deposition of lead in the urban environment of a Pb-Zn refinery was investigated, as a study case, using transient ("short-lived") isotopic signatures of the industrial source. Sampling campaigns were achieved in representative weather conditions, on an 8-h basis. Dry deposition rates measured downwind from refinery emissions (≈102-103 μg Pb m-2 h-1), cross-sectionally in a 3-5 km radius area around the plant, represent 10-100 times the urban background dry fallout, measured upwind, as well as fallout measured near other potential sources of anthropogenic Pb. The Pb-Zn refinery isotopic signature (approx. 1.100<206Pb/207Pb<1.135) is made identifiable, using the same set of Pb and Zn ores for 2 days before sampling and during field experiments, by agreement with the executive staff of the plant. This source signature is less radiogenic than signatures of urban background Pb aerosols (1.155<206Pb/207Pb<1.165) and minor sources of Pb aerosols (1.147<206Pb/207Pb<1.165). By a simple binary mixing model calculation, we established the extension of the industrial Pb deposition plume. Fifty to eighty percents of total lead settled by the dry deposition mode, 3-4 km away from the refinery, still have an industrial origin. That represents from 40 to 80 μg Pb m-2 h-1, in an area where the blood lead level exceeds 100 μg Pb l-1 for 30% of men and 12% of women living there. We demonstrate here that stable Pb isotope analysis is able to evidence the Pb dry deposition plume in stabilised aerodynamic conditions, using a short-lived source term, suggesting that this methodology is able to furnish valuable data to validate industrial Pb aerosols dispersion models, at the urban scale.

Synthesis of ZnO Nanocrystal-Graphene Composite by Mechanical Milling and Sonication-Assisted Exfoliation

NASA Astrophysics Data System (ADS)

Arora, Sweety; Srivastava, Chandan

2017-02-01

A ZnO nanocrystal-graphene composite was synthesized by a two-step method involving mechanical milling and sonication-assisted exfoliation. Zn metal powder was first ball-milled with graphite powder for 30 h in water medium. This ball-milled mixture was then subjected to exfoliation by sonication in the presence of sodium lauryl sulfate surfactant to produce graphene decorated with spherical agglomerates of ultrafine nanocrystalline ZnO. The presence of a few layers of graphene was confirmed by Raman spectroscopy and atomic force microscopy measurements. The size, phase identity and composition of the ZnO nanocrystals was determined by transmission electron microscopy measurements.

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.

Application of isotope dilution inductively coupled plasma mass spectrometry to the analysis of marine sediments

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

McLaren, J.W.; Beauchemin, D.; Berman, S.S.

1987-02-15

Isotope dilution inductively coupled plasma mass spectrometry (ICP-MS) has been applied to the determination of 11 trace elements (Cr, Ni, Zn, Sr, Mo, Cd, Sn, Sb, Tl, Pb, and U) in the marine sediment reference materials MESS-1 and BCSS-1. Accuracy and, especially, precision are better than those that can be easily achieved by other ICP-MS calibration strategies, as long as isotopic equilibration is achieved and the isotopes used for the ratio measurement are free of isobaric interferences by molecular species. The measurement of the isotope ratios on unspiked samples provides a sensitive diagnostic of such interferences.

Formation of a low-crystalline Zn-silicate in a stream in SW Sardinia, Italy

USGS Publications Warehouse

Wanty, Richard B.; De Giudici, G.; Onnis, P.; Rutherford, D.; Kimball, B.A.; Podda, F.; Cidu, R.; Lattanzi, P.; Medas, D.

2013-01-01

n southwestern Sardinia, Italy, the Rio Naracauli drains a catchment that includes several abandoned mines. The drainage from the mines and associated waste rocks has led to extreme concentrations of dissolved Zn, but because of the near-neutral pH, concentrations of other metals remain low. In the reach from approximately 2300 to 3000 m downstream from the headwaters area, an amorphous Zn-silicate precipitates from the water. In this reach, concentrations of both Zn and silica remain nearly constant, but the loads (measured in mass/time) of both increase, suggesting that new Zn and silica are supplied to the stream, likely from emerging groundwater. Zinc isotope signatures of the solid are heavier than the dissolved Zn by about 0.5 permil in 66/64Zn, suggesting that an extracellular biologically mediated adsorption process may be involved in the formation of the Zn-silicate.

Effect of process conditions and chemical composition on the microstructure and properties of chemically vapor deposited SiC, Si, ZnSe, ZnS and ZnS(x)Se(1-x)

NASA Technical Reports Server (NTRS)

Pickering, Michael A.; Taylor, Raymond L.; Goela, Jitendra S.; Desai, Hemant D.

1992-01-01

Subatmospheric pressure CVD processes have been developed to produce theoretically dense, highly pure, void-free and large area bulk materials, SiC, Si, ZnSe, ZnS and ZnS(x)Se(1-x). These materials are used for optical elements, such as mirrors, lenses and windows, over a wide spectral range from the VUV to the IR. We discuss the effect of CVD process conditions on the microstructure and properties of these materials, with emphasis on optical performance. In addition, we discuss the effect of chemical composition on the properties of the composite material ZnS(x)Se(1-x). We first present a general overview of the bulk CVD process and the relationship between process conditions, such as temperature, pressure, reactant gas concentration and growth rate, and the microstructure, morphology and properties of CVD-grown materials. Then we discuss specific results for CVD-grown SiC, Si, ZnSe, ZnS and ZnS(x)Se(1-x).

Piezoelectric and mechanical properties of fatigue resistant, self-healing PZT-ionomer composites

NASA Astrophysics Data System (ADS)

James, N. K.; Lafont, U.; van der Zwaag, S.; Groen, W. A.

2014-05-01

Piezoelectric ceramic-polymer composites with 0-3 connectivity were fabricated using lead zirconium titanate (PZT) powder dispersed in an ionomer (Zn ionomer) and its reference ethylene methacrylic acid copolymer (EMAA) polymer matrix. The PZT-Zn ionomer and PZT-EMAA composites were prepared by melt extrusion followed by hot pressing. The effects of poling conditions such as temperature, time and electric field on the piezoelectric properties of the composites were investigated. The experimentally observed piezoelectric charge coefficient and dielectric constant of the composites were compared with theoretical models. The results show that PZT-Zn ionomer composites have better piezoelectric properties compared to PZT-EMAA composites. The static and fatigue properties of the composites were investigated. The PZT-Zn ionomer composites were found to have excellent fatigue resistance even at strain levels of 4%. Due to the self-healing capabilities of the ionomer matrix, the loss of piezoelectric properties after high strain tensile cyclic loading could be partially recovered by thermal healing.

Lead-Free KNbO3:xZnO Composite Ceramics.

PubMed

Lv, Xiang; Li, Zhuoyun; Wu, Jiagang; Xiao, Dingquan; Zhu, Jianguo

2016-11-09

It is a tough issue to develop dense and water resistant KNbO 3 ceramics due to high evaporation and hygroscopicity of K 2 O. Here, KNbO 3 :xZnO composite ceramics were used to successfully solve this problem, where ZnO particles were randomly distributed into a KNbO 3 matrix. The addition of ZnO hardly affects the phase structure of KNbO 3 , and moreover, the enhancement of electrical properties, thermal stability, and aging characteristics was observed in KNbO 3 :xZnO composite ceramics. The composites possessed the maximum d 33 of 120 ± 5 pC/N, which is superior to that of pure KNbO 3 (d 33 = 80 pC/N). More importantly, a strong water resistance and an aging-free characteristic were observed in KNbO 3 :0.4ZnO. This is the first time for KNbO 3 ceramics to simultaneously improve electrical properties and resolve the water-absorbing properties. We believe that these composite ceramics are promising for practical applications.

Sulfonated graphene oxide-ZnO-Ag photocatalyst for fast photodegradation and disinfection under visible light.

PubMed

Gao, Peng; Ng, Kokseng; Sun, Darren Delai

2013-11-15

Synthesis of efficient visible-light-driven photocatalyst is urgent but challenging for environmental remediation. In this work, for the first time, the hierarchical plasmonic sulfonated graphene oxide-ZnO-Ag (SGO-ZnO-Ag) composites were prepared through nanocrystal-seed-directed hydrothermal method combining with polyol-reduction process. The results indicated that SGO-ZnO-Ag exhibited much faster rate in photodegradation of Rhodamine B (RhB) and disinfection of Escherichia coli (E. coli), than ZnO, SGO-ZnO and ZnO-Ag. SGO-ZnO-Ag totally degraded RhB dye and kill 99% of E. coli within 20 min under visible light irradiation. The outstanding performances of SGO-ZnO-Ag were attributed to the synergetic merits of SGO sheets, ZnO nanorod arrays and Ag nanoparticles. Firstly, the light absorption ability of SGO-ZnO-Ag composite in the visible region was enhanced due to the surface plasmon resonance of Ag. In addition, the hierarchical structure of SGO-ZnO-Ag composite improved the incident light scattering and reflection. Furthermore, SGO sheets facilitated charge transfer and reduce electron-hole recombination rate. Finally, the tentative mechanism was proposed and verified by the photoluminescence (PL) measurement as well as the theoretical finite-difference time-domain (FDTD) simulation. In view of above, this work paves the way for preparation of multi-component plasmonic composites and highlights the potential applications of SGO-ZnO-Ag in photocatalytic wastewater treatment field. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

Sediment-hosted Pb-Zn Deposits: a global perspective

USGS Publications Warehouse

Leach, David L.; Sangster, Donald F.; Kelley, Karen D.; Large, R; Garven, G.; Allen, Craig R.

2005-01-01

Sediment-hosted Pb-Zn deposits contain the world's greatest lead and zinc resources and dominate world production of these metals. They are a chverse group of ore deposits hosted by a wide variety of carbonate and siliciclastic roch that have no obviolls genetic association with igneous activity. A nmge of ore-fortl1ing processes in a vmiety of geologic and tectonic environments created these deposits over at least two billion years of Earth history. The metals were precipitated by basinal brines in synsedimentary and early diagenetic to low-grade metamorphic environments. The deposits display a broad range of relationships to enclosing host rocks that includes stratiform, strata-bound, and discordant ores. These ores are divided into two broad subt)1Jes: Mississippi Valley-type (MVT) and sedimentmy exhalative (SEDEX), Despite the "exhalative" component inherent in the term "SEDEX," in this manusclipt, direct evidence of an exhalite in the ore or alteration component is not essential for a deposit to be classified as SEDEX. The presence of laminated sulfides parallel to bedding is assumed to be permissive evidence for exhalative ores. The chstinction between some SEDEX and MVT depOSits can be quite subjective because some SEDEX ores replaced carbonate, whereas some MVT depOSits formed in an early diagenetic environment and display laminated ore textures. Geologic and resource information are presented for 248 depositS that provide a framework to describe ,mel compare these deposits. Nine of tlle 10 largest sediment-hosted Pb-Zn deposits are SEDEX, Of the deposits that contain at least 2.5 million metric tons (Mt), there are 35 SEDEX (excluding Broken Hill-type) deposits and 15 MVT (excluding Iris-type) deposits. Despite the skewed distribution of the deposit size, the two deposits types have an excellent correlation between total tonnage and tonnage of contained metal (Pb + Zn), with a fairly consistent ratio of about lO/l, regardless of the size of the deposit or district. Zinc grades are approximately the same for both, whereas Pb and Ag grades are about 25 percent greater for SEDEX deposits. The largest difference between SEDEX and MVT deposits is their Cu content. Three times as many SEDEX deposits have reported Cu contents, and the median Cu value of SEDEX deposits is nearly double that of MVT deposits. Furthermore, grade-tonnage values for MVT deposits compared to a subset of SEDEX deposits hosted in carbonate rocks are virtually indistinguishable. The distribution of MVT deposits through geologic time shows that they are mainly a Phanerozoic phenomenon. The ages of SEDEX deposits are grouped into two major groups, one in the Proterozoic and another in the Phanerozoic, MVT deposits dominantly formed in platform carbonate sequences typically located within extensional zones inboard of orogenic belts, whereas SEDEX deposits formed in intracontinental or failed rifts, and rifted continental margins. The ages of MVT ores are generally tens of millions of years younger than their host rocks; however, a few are close <~5 m.y.) to the age of their host rocks. In the absence of direct dates for SEDEX deposits, their age of formation is generally constnuned by relationships to sedimentary or diagenetic features in the rocks. These studies suggest that deposition of SEDEX ores was coeval with sedimentation or early diagenesis, whereas some deposits formed at least 20 m.y. after sedimentation. Fluid inclusion, isotopic studies, and deposit modeling suggest that MVf and SEDEX deposits formed from basin brines with similar temperatures of mainly 90° to 200°C and lO to 30 wt percent NaCI equiv. Lead isotope compositions for MVT and SEDEX deposits show that Pb was mainly derived from a variety of crustal sources. Lead isotope compositions do not provide critelia that distinguish MVT from SEDEX subtypes. However, sulfur isotope compositions for sphalerite and galena show an apparent difference. SEDEX and MVf sulfur isotope compositions extend over a large range; however, most data for SEDEX ores have mainly positive isotopic compositions from 0 to 20 per mil. Isotopic values for MVf ores extend over a wider range and include more data with negative isotopic values. Given that there are relatively small differences between the metal character of MVT and SEDEX deposits and the fluids that deposited them, perhaps the most significant difference between these deposits is their depositional environment, which is determined by their respective tectonic settings. The contrasting tectonic setting also dictates the fundamental deposit attributes that generally set them apart, such as host-rock lithology, deposit morphology, and ore textures. Blief discussions are also presented on two controversial sets of deposits: Broken Hill-type deposits and a subset of deposits in the MVT group located in the Irish Midlands, considered by some authors to be a distinct ore type (Irish type). There are no Significant differences in grade tonnage values between MVT deposits and the subset that is described as Irish type. Most features of the Irish deposits are not distinct from the family of MVT deposits; however, the age of mineralization that is the same as or close to the age of the host rocks and the anomalously high fluid inclusion temperatures (up to 250°C) stand out as distinctly different from typical MVT ores. The dominance of bacteriogenic sulfur in the hish ores commonly ascribed as uniquely hish type is in fact no different from several MVT deposits or districts. A comparison of SEDEX and Broken Hill-type deposits shows that the latter deposits contain signiflcantly higher contents of Ag and Pb relative to SEDEX deposits. In terms of median values, Broken Hill-type deposits are almost three times more ellliched in Ag and one and a half times more enriched in Pb compared to other SEDEX deposits. Metamorphism is a charactelisoc feature but not a prerequisite for inclusion in the Broken Hill-type category, and IGlown Broken Hill-type examples appear to occur in Paleo- to Mesoproterozoic terranes. Broken Hill-type deposits remain an enigmatic grouping; however, there is sufficient evidence to support their inclusion as a separate category of SEDEX deposits.

A vanadium-doped ZnO nanosheets-polymer composite for flexible piezoelectric nanogenerators

NASA Astrophysics Data System (ADS)

Shin, Sung-Ho; Kwon, Yang Hyeog; Lee, Min Hyung; Jung, Joo-Yun; Seol, Jae Hun; Nah, Junghyo

2016-01-01

We report high performance flexible piezoelectric nanogenerators (PENGs) by employing vanadium (V)-doped ZnO nanosheets (NSs) and the polydimethylsiloxane (PDMS) composite structure. The V-doped ZnO NSs were synthesized to overcome the inherently low piezoelectric properties of intrinsic ZnO. Ferroelectric phase transition induced in the V-doped ZnO NSs contributed to significantly improve the performance of the PENGs after the poling process. Consequently, the PENGs exhibited high output voltage and current up to ~32 V and ~6.2 μA, respectively, under the applied strain, which are sufficient to directly turn on a number of light emitting diodes (LEDs). The composite approach for PENG fabrication is scalable, robust, and reproducible during periodic bending/releasing over extended cycles. The approach introduced here extends the performance limits of ZnO-based PENGs and demonstrates their potential as energy harvesting devices.We report high performance flexible piezoelectric nanogenerators (PENGs) by employing vanadium (V)-doped ZnO nanosheets (NSs) and the polydimethylsiloxane (PDMS) composite structure. The V-doped ZnO NSs were synthesized to overcome the inherently low piezoelectric properties of intrinsic ZnO. Ferroelectric phase transition induced in the V-doped ZnO NSs contributed to significantly improve the performance of the PENGs after the poling process. Consequently, the PENGs exhibited high output voltage and current up to ~32 V and ~6.2 μA, respectively, under the applied strain, which are sufficient to directly turn on a number of light emitting diodes (LEDs). The composite approach for PENG fabrication is scalable, robust, and reproducible during periodic bending/releasing over extended cycles. The approach introduced here extends the performance limits of ZnO-based PENGs and demonstrates their potential as energy harvesting devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07185b

A novel approach reveals that zinc oxide nanoparticles are bioavailable and toxic after dietary exposures

USGS Publications Warehouse

Croteau, M.-N.; Dybowska, A.D.; Luoma, S.N.; Valsami-Jones, E.

2011-01-01

If engineered nanomaterials are released into the environment, some are likely to end up associated with the food of animals due to aggregation and sorption processes. However, few studies have considered dietary exposure of nanomaterials. Here we show that zinc (Zn) from isotopically modified 67ZnO particles is efficiently assimilated by freshwater snails when ingested with food. The 67Zn from nano-sized 67ZnO appears as bioavailable as 67Zn internalized by diatoms. Apparent agglomeration of the zinc oxide (ZnO) particles did not reduce bioavailability, nor preclude toxicity. In the diet, ZnO nanoparticles damage digestion: snails ate less, defecated less and inefficiently processed the ingested food when exposed to high concentrations of ZnO. It was not clear whether the toxicity was due to the high Zn dose achieved with nanoparticles or to the ZnO nanoparticles themselves. Further study of exposure from nanoparticles in food would greatly benefit assessment of ecological and human health risks. ?? 2011 Informa UK, Ltd.

Overview of the mechanisms that could explain the 'Boundary Exchange' at the land-ocean contact.

PubMed

Jeandel, Catherine

2016-11-28

Land to ocean transfer of material largely controls the chemical composition of seawater and the global element cycles. Oceanic isotopic budgets of chemical species, macro- and micronutrients (e.g. Nd, Sr, Si, Mg, Zn, Mo and Ni) have revealed an imbalance between their sources and sinks. Radiogenic isotope budgets underlined the importance of taking into account continental margins as a source of elements to oceans. They also highlighted that the net land-ocean inputs of chemical species probably result from particle-dissolved exchange processes, named 'Boundary Exchange'. Yet, locations where 'Boundary Exchange' occurs are not clearly identified and reviewed here: discharge of huge amount of freshly weathered particles at the river mouths, submarine weathering of deposited sediments along the margins, submarine groundwater discharges and subterranean estuaries. As a whole, we conclude that all of them might contribute to 'Boundary Exchange'. Highlighting their specific roles and the processes at play is a key scientific issue for the second half of GEOTRACES.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'. © 2016 The Author(s).

Overview of the mechanisms that could explain the ‘Boundary Exchange’ at the land–ocean contact

PubMed Central

2016-01-01

Land to ocean transfer of material largely controls the chemical composition of seawater and the global element cycles. Oceanic isotopic budgets of chemical species, macro- and micronutrients (e.g. Nd, Sr, Si, Mg, Zn, Mo and Ni) have revealed an imbalance between their sources and sinks. Radiogenic isotope budgets underlined the importance of taking into account continental margins as a source of elements to oceans. They also highlighted that the net land–ocean inputs of chemical species probably result from particle-dissolved exchange processes, named ‘Boundary Exchange’. Yet, locations where ‘Boundary Exchange’ occurs are not clearly identified and reviewed here: discharge of huge amount of freshly weathered particles at the river mouths, submarine weathering of deposited sediments along the margins, submarine groundwater discharges and subterranean estuaries. As a whole, we conclude that all of them might contribute to ‘Boundary Exchange’. Highlighting their specific roles and the processes at play is a key scientific issue for the second half of GEOTRACES. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’. PMID:29035253

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.

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

Collective nature of low-lying excitations in 70,72,74Zn from lifetime measurements using the AGATA spectrometer demonstrator

NASA Astrophysics Data System (ADS)

Louchart, C.; Obertelli, A.; Görgen, A.; Korten, W.; Bazzacco, D.; Birkenbach, B.; Bruyneel, B.; Clément, E.; Coleman-Smith, P. J.; Corradi, L.; Curien, D.; de Angelis, G.; de France, G.; Delaroche, J.-P.; Dewald, A.; Didierjean, F.; Doncel, M.; Duchêne, G.; Eberth, J.; Erduran, M. N.; Farnea, E.; Finck, C.; Fioretto, E.; Fransen, C.; Gadea, A.; Girod, M.; Gottardo, A.; Grebosz, J.; Habermann, T.; Hackstein, M.; Huyuk, T.; Jolie, J.; Judson, D.; Jungclaus, A.; Karkour, N.; Klupp, S.; Krücken, R.; Kusoglu, A.; Lenzi, S. M.; Libert, J.; Ljungvall, J.; Lunardi, S.; Maron, G.; Menegazzo, R.; Mengoni, D.; Michelagnoli, C.; Million, B.; Molini, P.; Möller, O.; Montagnoli, G.; Montanari, D.; Napoli, D. R.; Orlandi, R.; Pollarolo, G.; Prieto, A.; Pullia, A.; Quintana, B.; Recchia, F.; Reiter, P.; Rosso, D.; Rother, W.; Sahin, E.; Salsac, M.-D.; Scarlassara, F.; Schlarb, M.; Siem, S.; Singh, P. P.; Söderström, P.-A.; Stefanini, A. M.; Stézowski, O.; Sulignano, B.; Szilner, S.; Theisen, Ch.; Ur, C. A.; Valiente-Dobón, J. J.; Zielinska, M.

2013-05-01

Background: Neutron-rich nuclei with protons in the fp shell show an onset of collectivity around N=40. Spectroscopic information is required to understand the underlying mechanism and to determine the relevant terms of the nucleon-nucleon interaction that are responsible for the evolution of the shell structure in this mass region.Methods: We report on the lifetime measurement of the first 2+ and 4+ states in 70,72,74Zn and the first 6+ state in 72Zn using the recoil distance Doppler shift method. The experiment was carried out at the INFN Laboratory of Legnaro with the AGATA demonstrator, first phase of the Advanced Gamma Tracking Array of highly segmented, high-purity germanium detectors coupled to the PRISMA magnetic spectrometer. The excited states of the nuclei of interest were populated in the deep inelastic scattering of a 76Ge beam impinging on a 238U target.Results: The maximum of collectivity along the chain of Zn isotopes is observed for 72Zn at N=42. An unexpectedly long lifetime of 20-5.2+1.8 ps was measured for the 4+ state in 74Zn.Conclusions: Our results lead to small values of the B(E2;41+→21+)/B(E2;21+→01+) ratio for 72,74Zn, suggesting a significant noncollective contribution to these excitations. These experimental results are not reproduced by state-of-the-art microscopic models and call for lifetime measurements beyond the first 2+ state in heavy zinc and nickel isotopes.

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.

Facile preparation of well-combined lignin-based carbon/ZnO hybrid composite with excellent photocatalytic activity

NASA Astrophysics Data System (ADS)

Wang, Huan; Qiu, Xueqing; Liu, Weifeng; Yang, Dongjie

2017-12-01

In this work, a novel lignin-based carbon/ZnO (LC/ZnO) hybrid composite with excellent photocatalytic performance was prepared through a convenient and environment friendly method using alkali lignin (AL) as carbon source. The morphological, microstructure and optical properties of the as-prepared LC/ZnO hybrid composite was characterized with scanning electron microscope (SEM), X-ray diffraction (XRD), Raman and UV-vis. The resulting LC/ZnO hybrid is composed of highly dispersed ZnO nanoparticles embedded on a lignin-based carbon nanosheet, showing excellent photogenerated electrons and holes separation and migration efficiency. The photocatalytic activity of LC/ZnO was much higher than the pure ZnO. The LC/ZnO hybrid composite showed different photocatalytic mechanism for degradation of negative methyl orange (MO) and positive Rhodamine B (RhB). It showed that h+ was the main photocatalytic active group during the degradation of MO, ·O2- and ·OH were the photocatalytic active groups during degradation of RhB. This reported photocatalyst with selective degradation of positive and negative organic dyes may have a great application prospect for photoelectric conversion and catalytic materials. Results of this work were of practical importance for high-valued utilization of lignin for carbon materials.

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.

MIRA: A new approach to measuring Δ $47 in carbonates and geothermometry of MVT type deposits

NASA Astrophysics Data System (ADS)

Dennis, P. F.; Vinen, S. J.

2009-04-01

Clumped isotope thermometry is based on the thermodynamics of the order-disorder reaction for 18O and 13C: 13C16O16O16O + 12C18O16O16O = 13C18O16O16O + 12C16O16O16O At high temperatures 18O is randomly distributed between 12C and 13C in the carbonate anion. However, at lower temperatures there is a tendency for the 18O to cluster together with 13C. At low temperatures (T < 150oC) the degree of ordering, as measured by 47 of the CO2 that is produced by reaction of the carbonate with phosphoric acid ((13C18O16Osample/13C18O16Ostochastic)-1) is a potentially useful geothermometer (Eiler, 2007). However, for reliable temperature estimates to better than +/- 1oC at near earth surface temperatures requires measurement of 1000*47 to better than +/-0.005. Given that the 47 isotopologue occurs at a natural abundance of just 40ppm in CO2 this is a challenging measurement for stable isotope ratio mass spectrometry. We have developed a new instrument MIRA to accurately measure such small isotope ratios. MIRA is configured with a 50cm dispersion analyser, dual inlet, a high sensitivity Nier type source, 6 faraday collectors at m/z = 44, 45, 46, 47, 48 and 49 and ultra stable and linear detection and integration electronics. Using a dual inlet measurement precisions for 1000*47 are better than +/-0.01. To date isotopic clusters have just been used to estimate near surface and diagenetic temperatures to 75oC. We are using MIRA and the clumped isotope thermometer to assess formation temperatures (up to 150oC) and the timing of MVT Pb/Zn mineralisation in the Pennines, UK orefield. Because temperature estimates are based on an internal order-disorder reaction, they are independent of the isotopic composition of the formation waters making it possible independently to track changes in the ^18O composition of mineralising fluids. With sufficient resolution (+/- 2 - 5oC) we aim to map temperature distributions in order to better constrain the hydrothermal system. This is the first application of clumped isotopes to 'elevated' temperature thermometry. Eiler, J.M., 2007, 'Clumped-isotope' geochemistry - The study of naturally occurring multiply substituted isotopologues. Earth and Planetary Science Letters, 262, 309-327

Synthesis of zinc ferrite/silver iodide composite with enhanced photocatalytic antibacterial and pollutant degradation ability.

PubMed

Xu, Yuanguo; Liu, Qingqing; Xie, Meng; Huang, Shuquan; He, Minqiang; Huang, Liying; Xu, Hui; Li, Huaming

2018-05-22

ZnFe 2 O 4 /AgI composites were first prepared successfully with a hydrothermal method, and ZnFe 2 O 4 nanoparticles were uniformly decorated on the surface of AgI particles. The photocatalytic activities of the obtained ZnFe 2 O 4 /AgI composites were investigated by the degradation of organic pollutants and the inactivation of bacteria under visible light irradiation. The results showed that the introduction of ZnFe 2 O 4 greatly enhanced the light harvesting ability and improved the separation efficiency of the photogenerated charge carriers, which contributed to the enhanced generation of reactive species and thus promoted the photocatalytic performance. The 5% ZnFe 2 O 4 /AgI composite exhibited the optimal photocatalytic disinfection of E. coli (100% removal efficiency in 80 min) as well as the photocatalytic degradation of rhodamine B (RhB) (98.5% removal rate in 40 min). Furthermore, four consecutive cycles also demonstrated the stable photocatalytic activity of the as-prepared ZnFe 2 O 4 /AgI composites. In addition, H 2 O 2 was identified as the predominant active species in the photocatalytic inactivation of bacteria. This study indicated that ZnFe 2 O 4 /AgI composites are a promising candidate for the treatment of wastewater. Copyright © 2018 Elsevier Inc. All rights reserved.

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.

Incorporation of zinc for fabrication of low-cost spinel-based composite ceramic membrane support to achieve its stabilization.

PubMed

Li, Lingling; Dong, Xinfa; Dong, Yingchao; Zhu, Li; You, Sheng-Jie; Wang, Ya-Fen

2015-04-28

In order to reduce environment risk of zinc, a spinel-based porous membrane support was prepared by the high-temperature reaction of zinc and bauxite mineral. The phase evolution process, shrinkage, porosity, mechanical property, pore size distribution, gas permeation flux and microstructure were systematically studied. The XRD results, based on a Zn/Al stoichiometric composition of 1/2, show a formation of ZnAl2O4 structure starting from 1000°C and then accomplished at 1300°C. For spinel-based composite membrane, shrinkage and porosity are mainly influenced by a combination of an expansion induced by ZnAl2O4 formation and a general densification due to amorphous liquid SiO2. The highest porosity, as high as 44%, is observed in ZnAl4 membrane support among all the investigated compositions. Compared with pure bauxite (Al), ZnAl4 composite membrane support is reinforced by ZnAl2O4 phase and inter-locked mullite crystals, which is proved by the empirical strength-porosity relationships. Also, an increase in average pore diameter and gas flux can be observed in ZnAl4. A prolonged leaching experiment reveals the zinc can be successfully incorporated into ceramic membrane support via formation of ZnAl2O4, which has substantially better resistance toward acidic attack. Copyright © 2015 Elsevier B.V. All rights reserved.

Fabrication of hierarchical porous ZnO-Al2O3 microspheres with enhanced adsorption performance

NASA Astrophysics Data System (ADS)

Lei, Chunsheng; Pi, Meng; Xu, Difa; Jiang, Chuanjia; Cheng, Bei

2017-12-01

Hierarchical porous ZnO-Al2O3 microspheres were fabricated through a simple hydrothermal route. The as-prepared hierarchical porous ZnO-Al2O3 composites were utilized as adsorbents to remove organic dye Congo red (CR) from water. The ZnO-Al2O3 composites had morphology of microspheres with diameters in the range of 12-16 μm, which were assembled by nanosheets with thicknesses of approximately 60 nm. The adsorption kinetics of CR onto the ZnO-Al2O3 composites was properly fitted by the pseudo-second-order kinetic model. The equilibrium adsorption data were perfectly described by the Langmuir isotherm and had a maximum adsorption capacity that reached 397 mg/g, which was significantly higher than the value of the pure alumina (Al2O3) and zinc oxide (ZnO) samples. The superior CR removal efficiency of the ZnO-Al2O3 composites was attributed to its well-developed hierarchical porous structures and larger specific surface area (201 m2/g), which were conducive to the diffusion and adsorption of CR molecules. Moreover, the regeneration study reveals that the ZnO-Al2O3 composites have suitable stability and reusability. The results also indicate that the as-prepared sample can act as a highly effective adsorbent in anionic dye removal from wastewater.

Study of structural and optical properties of ZnAlQ5 (zinc aluminum quinolate) organic phosphor for OLED applications

NASA Astrophysics Data System (ADS)

Nagpure, I. M.; Painuly, Deepshikha; Rabanal, Maria Eugenia

2016-05-01

The various composition of ZnAlQ5 such as Zn1.5A10.5Q5, Zn1Al1Q5, Zn0.5Al1.5Q5 organic phosphors were prepared via simple cost effective co-precipitation method. The FTIR, SEM, photoluminescence analysis of the prepared phosphors were reported. ZnQ2 and AlQ3 were also prepared by similar method and their properties were compared with different composition of ZnAlQ5. The structural elucidation in the form of stretching frequencies of chemical bonds of the prepared phosphor was carried out using Fourier Transform Infrared Spectroscopy (FTIR). The stretching frequency analysis confirms the formation of prepared phosphor materials. The SEM analysis shows the surface morphological behavior of prepared phosphor materials. Greenish photoluminescence were observed at 505 to 510 nm for the different composition of ZnAlQ5,in which Zn1.5Al0.5Q5 shows maximum luminescence intensity at 505 nm. PL emission of ZnQ2 was observed at 515 nm, while for AlQ3 at 520 nm. The blue shift of 10 nm was observed in Zn1.5A10.5Q5 due to modification of energy level due to presence of Zn2+ and Al3+. The enhancement in PL intensity was observed in Zn1.5A10.5Q5 compared to the other composition due to transfer of energy between Zn2+ and quinolate complex. Optical properties of the prepared materials were evaluated for possible applications in organic light emitting devices (OLED).

Study of white light emission from ZnS/PS composite system

NASA Astrophysics Data System (ADS)

Wang, Caifeng; Li, Qingshan; Lu, Lei; Zhang, Lichun; Qi, Hongxia

2007-09-01

ZnS films were deposited by pulsed laser deposition (PLD) on porous silicon (PS) substrates formed by electrochemical anodization of p-type (100) silicon wafer. The photoluminescence (PL) spectra of ZnS/PS composites were measured at room temperature. Under different excitation wavelengths, the relative integrated intensities of the red light emission from PS layers and the blue-green emission from ZnS films had different values. After samples were annealed in vacuum at different temperatures (200, 300, and 400 Celsius degree) for 30 min respectively, a new green emission located at around 550 nm appeared in the PL spectra of all ZnS/PS samples, and all of the ZnS/PS composites had a broad PL band (450-700 nm) in the visible region, exhibiting intensively white light emission.

Photocatalytic degradation of organic dyes by Er3+: YAlO3/Co- and Fe-doped ZnO coated composites under solar irradiation

NASA Astrophysics Data System (ADS)

Chen, Yang; Lu, Chunxiao; Tang, Liang; Song, Yahui; Wei, Shengnan; Rong, Yang; Zhang, Zhaohong; Wang, Jun

2016-12-01

In this work, the Er3+: YAlO3/Co- and Fe-doped ZnO coated composites were prepared by the sol-gel method. Then, they were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDX). Photo-degradation of azo fuchsine (AF) as a model dye under solar light irradiation was studied to evaluate the photocatalytic activity of the Er3+: YAlO3/Co- and Fe-doped ZnO coated composites. It was found that the photocatalytic activity of Co- and Fe-doped ZnO composites can be obviously enhanced by upconversion luminescence agent (Er3+: YAlO3). Besides, the photocatalytic activity of Er3+: YAlO3/Fe-doped ZnO is better than that of Er3+: YAlO3/Co-doped ZnO. The influence of experiment conditions, such as the concentration of Er3+: YAlO3, heat-treatment temperature and time on the photocatalytic activity of the Er3+: YAlO3/Co- and Fe-doped ZnO coated composites was studied. In addition, the effects of solar light irradiation time, dye initial concentration, Er3+: YAlO3/Co- and Fe-doped ZnO amount on the photocatalytic degradation of azo fuchsine in aqueous solution were investigated in detail. Simultaneously, some other organic dyes, such as Methyl Orange (MO), Rhodamine B (RM-B), Acid Red B (AR-B), Congo Red (CR), and Methyl Blue (MB) were also studied. The possible excitation principle of Er3+: YAlO3/Co- and Fe-doped ZnO coated composites under solar light irradiation and the photocatalytic degradation mechanism of organic dyes were discussed.

Effect of calcination temperature on the photodegradation efficiency of Ni/ZnO composite in removal of organic dye

NASA Astrophysics Data System (ADS)

Thein, Myo Thuya; Pung, Swee-Yong; Aziz, Azizan; Lockman, Zainovia; Itoh, Mitsuru

2017-07-01

ZnO based composite is an attractive UV light driven semiconductor photocatalyst to degrade organic compounds attributed to its wide bandgap (3.37 eV). In this study, Ni/ZnO composites were synthesized via solution precipitation method. The composites were calcinated at various temperature, i.e. from 250 °C to 700 °C and subsequently annealed at 500°C in reductive environment (hydrogen atmosphere). The diffraction peaks of all samples could be indexed to the hexagonal wurtzite ZnO. No diffraction peaks from Ni could be observed in all samples, suggesting that the amount of Ni in the composites were below the detection limit of X-ray diffraction (XRD). The field emission scanning electron microscope (FESEM) images confirm that all samples were rod-like structure with hexagonal tips. In addition, small Ni particles were homogeneously deposited on the surface of ZnO rods. This observation is supported by energy dispersive X-ray spectroscopy (EDX) analysis, showing present of Zn, O and Ni elements. It is noted that ZnO rods coupled with Ni experienced quenching of visible emission and enhancing of UV emission in room temperature photoluminescence (RTPL) analysis. The photodegradation efficiency of Ni/ZnO rods was improved when a higher calcination temperature was used. The removal of RhB dye under UV light (352 nm) by these photocatalysts followed pseudo first-order kinetic reaction. The Ni/ZnO composites synthesized at calcination temperature of 500 °C demonstrated the highest photodegradation efficiency of 37 % and the largest rate constant of 0.0053 min-1 after 75 min UV irradiation.

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.

Intrinsic point defects in off-stoichiometric Cu2ZnSnSe4: A neutron diffraction study

NASA Astrophysics Data System (ADS)

Gurieva, Galina; Valle Rios, Laura Elisa; Franz, Alexandra; Whitfield, Pamela; Schorr, Susan

2018-04-01

This work is an experimental study of intrinsic point defects in off-stoichiometric kesterite type CZTSe by means of neutron powder diffraction. We revealed the existence of copper vacancies (VCu), various cation anti site defects (CuZn, ZnCu, ZnSn, SnZn, and CuZn), as well as interstitials (Cui, Zni) in a wide range of off-stoichiometric polycrystalline powder samples synthesized by the solid state reaction. The results show that the point defects present in off-stoichiometric CZTSe agree with the off-stoichiometry type model, assuming certain cation substitutions accounting for charge balance. In addition to the known off-stoichiometry types A-H, new types (I-L) have been introduced. For the very first time, a correlation between the chemical composition of the CZTSe kesterite type phase and the occurring intrinsic point defects is presented. In addition to the off-stoichiometry type specific defects, the Cu/Zn disorder is always present in the CZTSe phase. In Cu-poor/Zn-rich CZTSe, a composition considered as the one that delivers the best photovoltaic performance, mainly copper vacancies, ZnCu and ZnSn anti sites are present. Also, this compositional region shows the lowest degree of Cu/Zn disorder.

Fabrication of Well-Aligned ZnO Nanorods Using a Composite Seed Layer of ZnO Nanoparticles and Chitosan Polymer.

PubMed

Khun, Kimleang; Ibupoto, Zafar Hussain; AlSalhi, Mohamad S; Atif, Muhammad; Ansari, Anees A; Willander, Magnus

2013-09-30

In this study, by taking the advantage of both inorganic ZnO nanoparticles and the organic material chitosan as a composite seed layer, we have fabricated well-aligned ZnO nanorods on a gold-coated glass substrate using the hydrothermal growth method. The ZnO nanoparticles were characterized by the Raman spectroscopic techniques, which showed the nanocrystalline phase of the ZnO nanoparticles. Different composites of ZnO nanoparticles and chitosan were prepared and used as a seed layer for the fabrication of well-aligned ZnO nanorods. Field emission scanning electron microscopy, energy dispersive X-ray, high-resolution transmission electron microscopy, X-ray diffraction, and infrared reflection absorption spectroscopic techniques were utilized for the structural characterization of the ZnO nanoparticles/chitosan seed layer-coated ZnO nanorods on a gold-coated glass substrate. This study has shown that the ZnO nanorods are well-aligned, uniform, and dense, exhibit the wurtzite hexagonal structure, and are perpendicularly oriented to the substrate. Moreover, the ZnO nanorods are only composed of Zn and O atoms. An optical study was also carried out for the ZnO nanoparticles/chitosan seed layer-coated ZnO nanorods, and the obtained results have shown that the fabricated ZnO nanorods exhibit good crystal quality. This study has provided a cheap fabrication method for the controlled morphology and good alignment of ZnO nanorods, which is of high demand for enhancing the working performance of optoelectronic devices.

Fabrication of Well-Aligned ZnO Nanorods Using a Composite Seed Layer of ZnO Nanoparticles and Chitosan Polymer

PubMed Central

Khun, Kimleang; Ibupoto, Zafar Hussain; AlSalhi, Mohamad S.; Atif, Muhammad; Ansari, Anees A.; Willander, Magnus

2013-01-01

In this study, by taking the advantage of both inorganic ZnO nanoparticles and the organic material chitosan as a composite seed layer, we have fabricated well-aligned ZnO nanorods on a gold-coated glass substrate using the hydrothermal growth method. The ZnO nanoparticles were characterized by the Raman spectroscopic techniques, which showed the nanocrystalline phase of the ZnO nanoparticles. Different composites of ZnO nanoparticles and chitosan were prepared and used as a seed layer for the fabrication of well-aligned ZnO nanorods. Field emission scanning electron microscopy, energy dispersive X-ray, high-resolution transmission electron microscopy, X-ray diffraction, and infrared reflection absorption spectroscopic techniques were utilized for the structural characterization of the ZnO nanoparticles/chitosan seed layer-coated ZnO nanorods on a gold-coated glass substrate. This study has shown that the ZnO nanorods are well-aligned, uniform, and dense, exhibit the wurtzite hexagonal structure, and are perpendicularly oriented to the substrate. Moreover, the ZnO nanorods are only composed of Zn and O atoms. An optical study was also carried out for the ZnO nanoparticles/chitosan seed layer-coated ZnO nanorods, and the obtained results have shown that the fabricated ZnO nanorods exhibit good crystal quality. This study has provided a cheap fabrication method for the controlled morphology and good alignment of ZnO nanorods, which is of high demand for enhancing the working performance of optoelectronic devices. PMID:28788336

Preparation of Graphene-Zinc Oxide Nanostructure Composite for Carbon Monoxide Gas Sensing

NASA Astrophysics Data System (ADS)

Muchtar, Ahmad Rifqi; Septiani, Ni Luh Wulan; Iqbal, Muhammad; Nuruddin, Ahmad; Yuliarto, Brian

2018-03-01

A simple method to synthesize graphene-zinc oxide nanocomposite has been developed. A reduced graphene oxide-ZnO nanocomposite was prepared using a reflux method with ethylene glycol as medium. X-ray diffraction analysis, scanning electron microscopy, energy-dispersive spectrometry, and nitrogen adsorption-desorption measurements were used to characterize the resulting composite materials. The highest response of about 98% was observed when using pure ZnO at 300°C, while the second highest sensor response of about 96% was achieved by graphene-ZnO with 1:3 composition. It was found that the graphene-zinc oxide hybrid has potential to improve sensor performance at low temperature. The graphene-ZnO hybrid with 1:3 composition showed good response of 36% at 125°C, an operating temperature at which pure ZnO showed no response.

Preparation of Graphene-Zinc Oxide Nanostructure Composite for Carbon Monoxide Gas Sensing

NASA Astrophysics Data System (ADS)

Muchtar, Ahmad Rifqi; Septiani, Ni Luh Wulan; Iqbal, Muhammad; Nuruddin, Ahmad; Yuliarto, Brian

2018-07-01

A simple method to synthesize graphene-zinc oxide nanocomposite has been developed. A reduced graphene oxide-ZnO nanocomposite was prepared using a reflux method with ethylene glycol as medium. X-ray diffraction analysis, scanning electron microscopy, energy-dispersive spectrometry, and nitrogen adsorption-desorption measurements were used to characterize the resulting composite materials. The highest response of about 98% was observed when using pure ZnO at 300°C, while the second highest sensor response of about 96% was achieved by graphene-ZnO with 1:3 composition. It was found that the graphene-zinc oxide hybrid has potential to improve sensor performance at low temperature. The graphene-ZnO hybrid with 1:3 composition showed good response of 36% at 125°C, an operating temperature at which pure ZnO showed no response.

Diffusion, swelling, cross linkage study and mechanical properties of ZnO doped PVA/NaAlg blend polymer nanocomposite

NASA Astrophysics Data System (ADS)

Guruswamy, B.; Ravindrachary, V.; Shruthi, C.; Hegde, Shreedatta; Sagar, Rohan N.

2018-04-01

ZnO nano particles were synthesized using a chemical precipitation method. Pure and ZnO nano particle doped PVA-NaAlg blend composite films were prepared using solution casing method. Structural information of these composites was studied using FTIR. Diffusion kinetics of these polymer blend composite were studied using Flory-Huggins theory. Using these diffusion studies, cross-linking density and swelling properties of the films were analyzed. Mechanical properties of these composite are also studied.

Mobilisation of traffic-derived trace metals from road corridors into coastal stream and estuarine sediments, Cairns, northern Australia

NASA Astrophysics Data System (ADS)

Pratt, C.; Lottermoser, B. G.

2007-04-01

This investigation revealed the presence of traffic-derived metals within road, stream and estuarine sediments collected from a coastal catchment, northern Australia. Studied road sediments displayed variable total metal concentrations (median Cd, Cu, Pb, Pd, Pt, Ni and Zn values: 0.19, 42.6, 67.5, 0.064, 0.104, 36.7 and 698 mg/kg, respectively). The distinctly elevated Zn values are due to abundant tyre rubber shreds (as verified by SEM-EDS and correlation analysis). By comparison to the road sediments, background stream sediments taken upstream from roads have relatively low median Pb, Pd, Pt and Zn concentrations (7.3 mg/kg Pb, 0.01 mg/kg Pd, 0.012 mg/kg Pt, 62 mg/kg Zn). Stream and estuarine sediment samples collected below roads have median values of 21.8 mg/kg Pb, 0.014 mg/kg Pd, 0.021 mg/kg Pt and 71 mg/kg Zn, and exhibit 207Pb/206Pb and 208Pb/206Pb ratios that appear on a mixing line between the isotopically distinct background stream sediments and the road sediments. Thus, mobilisation of dusts and sediments from road surfaces has resulted in relatively elevated Pb, Pd, Pt and Zn concentrations and non-radiogenic Pb isotope ratios in local coastal stream and estuarine sediments. The investigation demonstrates that traffic-derived metals enter coastal stream and estuary sediments at the fringe of the Great Barrier Reef lagoon.

Characterization of high-purity 82Se-enriched ZnSe for double-beta decay bolometer/scintillation detectors

NASA Astrophysics Data System (ADS)

Silva, B. C.; de Oliveira, R.; Ribeiro, G. M.; Cury, L. A.; Leal, A. S.; Nagorny, S.; Krambrock, K.

2018-02-01

Zinc selenide (ZnSe), when enriched with 82Se isotope, is one of the most promising materials for the construction of a bolometer/scintillation detector to study neutrinoless double beta decay (0νDBD). Because the 0νDBD is a very rare event, a high quantity of high-purity monocrystalline ZnSe is needed, which means high costs. Therefore, the knowledge of the best material parameters, especially the presence of point defects, is essential to make feasible the construction of such a detector. In this work, both the as-grown and thermally annealed ZnSe enriched to 95% with the 82Se isotope grown by the Bridgman technique from high-purity starting materials were characterized by electron paramagnetic resonance (EPR), photo-EPR, neutron activation, photoluminescence, and electrical measurements. It is shown that although thermal annealing increases crystal homogeneity and reduces microcracks, the scintillation efficiency is much better for the as-grown material. The higher scintillation efficiency is due to the presence of donor acceptor pairs in the as-grown material, which are responsible for strong luminescence/scintillation in the red spectral region. By photo-EPR, the donor acceptor pairs are identified as closed VZn - AlZn pairs which are lost during the annealing procedure. Electrical characterization shows that the as-grown material is of good quality as it has high electron mobility at low temperatures. Excellent material parameters for the construction of the bolometer/scintillation detector based on enriched Zn82Se are discussed.

Zinc Absorption from Representative Diet in a Chinese Elderly Population Using Stable Isotope Technique.

PubMed

Li, Ya Jie; Li, Min; Liu, Xiao Bing; Ren, Tong Xiang; Li, Wei Dong; Yang, Chun; Wu, Meng; Yang, Lin Li; Ma, Yu Xia; Wang, Jun; Piao, Jian Hua; Yang, Li Chen; Yang, Xiao Guang

2017-06-01

To determine the dietary zinc absorption in a Chinese elderly population and provide the basic data for the setting of zinc (Zn) recommended nutrient intakes (RNI) for Chinese elderly people. A total of 24 elderly people were recruited for this study and were administered oral doses of 3 mg 67Zn and 1.2 mg dysprosium on the fourth day. The primary macronutrients, energy, and phytic acid in the representative diet were examined based on the Chinese National Standard Methods. Fecal samples were collected during the experimental period and analyzed for zinc content, 67Zn isotope ratio, and dysprosium content. The mean (± SD) zinc intake from the representative Chinese diet was 10.6 ± 1.5 mg/d. The phytic acid-to-zinc molar ratio in the diet was 6.4. The absorption rate of 67Zn was 27.9% ± 9.2%. The RNI of zinc, which were calculated by the absorption rate in elderly men and women, were 10.4 and 9.2 mg/d, respectively. This study got the dietary Zn absorption in a Chinese elderly population. We found that Zn absorption was higher in elderly men than in elderly women. The current RNI in elderly female is lower than our finding, which indicates that more attention is needed regarding elderly females' zinc status and health. Copyright © 2017 The Editorial Board of Biomedical and Environmental Sciences. Published by China CDC. All rights reserved.

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.

Thallium dispersal and contamination in surface sediments from South China and its source identification.

PubMed

Liu, Juan; Wang, Jin; Chen, Yongheng; Shen, Chuan-Chou; Jiang, Xiuyang; Xie, Xiaofan; Chen, Diyun; Lippold, Holger; Wang, Chunlin

2016-06-01

Thallium (Tl) is a non-essential element in humans and it is considered to be highly toxic. In this study, the contents, sources, and dispersal of Tl were investigated in surface sediments from a riverine system (the western Pearl River Basin, China), whose catchment has been contaminated by mining and roasting of Tl-bearing pyrite ores. The isotopic composition of Pb and total contents of Tl and other relevant metals (Pb, Zn, Cd, Co, and Ni) were measured in the pyrite ores, mining and roasting wastes, and the river sediments. Widespread contamination of Tl was observed in the sediments across the river, with the highest concentration of Tl (17.3 mg/kg) measured 4 km downstream from the pyrite industrial site. Application of a modified Institute for Reference Materials and Measurement (IRMM) sequential extraction scheme in representative sediments unveiled that 60-90% of Tl and Pb were present in the residual fraction of the sediments. The sediments contained generally lower (206)Pb/(207)Pb and higher (208)Pb/(206)Pb ratios compared with the natural Pb isotope signature (1.2008 and 2.0766 for (206)Pb/(207)Pb and (208)Pb/(206)Pb, respectively). These results suggested that a significant fraction of non-indigenous Pb could be attributed to the mining and roasting activities of pyrite ores, with low (206)Pb/(207)Pb (1.1539) and high (208)Pb/(206)Pb (2.1263). Results also showed that approximately 6-88% of Tl contamination in the sediments originated from the pyrite mining and roasting activities. This study highlights that Pb isotopic compositions could be used for quantitatively fingerprinting the sources of Tl contamination in sediments. Copyright © 2016 Elsevier Ltd. All rights reserved.

Geochemical and oxygen isotope perspective of a new R chondrite Dhofar 1671: Affinity with ordinary chondrites

NASA Astrophysics Data System (ADS)

Ali, Arshad; Nasir, Sobhi J.; Jabeen, Iffat; Al Rawas, Ahmed; Banerjee, Neil R.; Osinski, Gordon R.

2017-09-01

Dhofar 1671 is a relatively new meteorite that previous studies suggest belongs to the Rumuruti chondrite class. Major and REE compositions are generally in agreement with average values of the R chondrites (RCs). Moderately volatile elements such as Se and Zn abundances are lower than the R chondrite values that are similar to those in ordinary chondrites (OCs). Porphyritic olivine pyroxene (POP), radial pyroxene (RP), and barred olivine (BO) chondrules are embedded in a proportionately equal volume of matrix, one of the characteristic features of RCs. Microprobe analyses demonstrate compositional zoning in chondrule and matrix olivines showing Fa-poor interior and Fa-rich outer zones. Precise oxygen isotope data for chondrules and matrix obtained by laser-assisted fluorination show a genetic isotopic relationship between OCs and RCs. On the basis of our data, we propose a strong affinity between these groups and suggest that OC chondrule precursors could have interacted with a 17O-rich matrix to form RC chondrules (i.e., ∆17O shifts from 1‰ to 3‰). These interactions could have occurred at the same time as "exotic" clasts in brecciated samples formed such as NWA 10214 (LL3-6), Parnallee (LL3), PCA91241 (R3.8-6), and Dhofar 1671 (R3.6). We also infer that the source of the oxidation and 17O enrichment is the matrix, which may have been enriched in 17O-rich water. The abundance of matrix in RCs relative to OCs, ensured that these rocks would be apparently more oxidized and appreciably 17O-enriched. In situ analysis of Dhofar 1671 is recommended to further strengthen the link between OCs and RCs.

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.

Compositions of Mg and Se, surface morphology, roughness and Raman property of Zn1-xMgxSeyTe1-y layers grown at various substrate temperatures or dopant transport rates by MOVPE

NASA Astrophysics Data System (ADS)

Nishio, Mitsuhiro; Saito, Katsuhiko; Urata, Kensuke; Okamoto, Yasuhiro; Tanaka, Daichi; Araki, Yasuhiro; Abiru, Masakatsu; Mori, Eiichiro; Tanaka, Tooru; Guo, Qixin

2015-03-01

The growth of undoped and phosphorus (P)-doped Zn1-xMgxSeyTe1-y layers on (100) ZnTe substrates by metalorganic vapor phase epitaxy was carried out. The compositions of Mg and Se, surface morphology, roughness and Raman property were characterized as a function of substrate temperature. Not only the compositions of Mg and Se but also the crystal quality of undoped Zn1-xMgxSeyTe1-y layer strongly depended upon the substrate temperature. Furthermore, the growth of Zn1-xMgxSeyTe1-y layer nearly-lattice-matched to ZnTe substrate was achieved independent of the transport rate of trisdimethylaminophosphorus. Undoped Zn1-xMgxSeyTe1-y layer nearly-lattice-matched to ZnTe led to improvement of surface roughness. On the other hand, P doping brought about deterioration of crystalline quality.

Hydrothermal synthesis of In2O3 nanoparticles hybrid twins hexagonal disk ZnO heterostructures for enhanced photocatalytic activities and stability

NASA Astrophysics Data System (ADS)

Liu, Hairui; Zhai, Haifa; Hu, Chunjie; Yang, Jien; Liu, Zhiyong

2017-07-01

In2O3 nanoparticles hybrid twins hexagonal disk (THD) ZnO with different ratios were fabricated by a hydrothermal method. The as-obtained ZnO/In2O3 composites are constituted by hexagonal disks ZnO with diameters of about 1 μm and In2O3 nanoparticles with sizes of about 20-50 nm. With the increase of In2O3 content in ZnO/In2O3 composites, the absorption band edges of samples shifted from UV to visible light region. Compared with pure ZnO, the ZnO/In2O3 composites show enhanced photocatalytic activities for degradation of methyl orange (MO) and 4-nitrophenol (4-NP) under solar light irradiation. Due to suitable alignment of their energy band-gap structure of the In2O3 and ZnO, the formation of type п heterostructure can enhance efficient separation of photo-generate electro-hole pairs and provides convenient carrier transfer paths.

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.

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.

Chemical composition and Zn bioavailability of the soil solution extracted from Zn amended variable charge soils.

PubMed

Zampella, Mariavittoria; Adamo, Paola

2010-01-01

A study on variable charge soils (volcanic Italian and podzolic Scottish soils) was performed to investigate the influence of soil properties on the chemical composition of soil solution. Zinc speciation, bioavailability and toxicity in the soil solution were examined. The soils were spiked with increasing amounts of Zn (0, 100, 200, 400 and 1000 mg/kg) and the soil solutions were extracted using rhizon soil moisture samplers. The pH, total organic carbon (TOC), base cations, anions, total Zn and free Zn2+ in soil solution were analysed. A rapid bioassay with the luminescent bacterium Escherichia coli HB101 pUCD607 was performed to assess Zn toxicity. The influence of soil type and Zn treatments on the chemical composition of soil solution and on Zn toxicity was considered and discussed. Different trends of total and free Zn concentrations, base cations desorption and luminescence of E. coli HB101 pUCD607 were observed. The soil solution extracted from the volcanic soils had very low total and free Zn concentrations and showed specific Zn2+/Ca2+ exchange. The soil solution from the podzolic soil had much higher total and free Zn concentrations and showed no evidence of specific Zn2+/Ca2+ exchange. In comparison with the subalkaline volcanic soils, the acidic podzol showed enhanced levels of toxic free Zn2+ and consequently stronger effects on E. coli viability.

Fabrication of a Nano-ZnO/Polyethylene/Wood-Fiber Composite with Enhanced Microwave Absorption and Photocatalytic Activity via a Facile Hot-Press Method

PubMed Central

Dang, Baokang; Chen, Yipeng; Shen, Xiaoping; Chen, Bo; Sun, Qingfeng; Jin, Chunde

2017-01-01

A polyethylene/wood-fiber composite loaded with nano-ZnO was prepared by a facile hot-press method and was used for the photocatalytic degradation of organic compounds as well as for microwave absorption. ZnO nanoparticles with an average size of 29 nm and polyethylene (PE) powders were dispersed on the wood fibers’ surface through a viscous cationic polyacrylamide (CPAM) solution. The reflection loss (RL) value of the resulting composite was −21 dB, with a thickness of 3.5 mm in the frequency of 17.17 GHz. The PE/ZnO/wood-fiber (PZW) composite exhibited superior photocatalytic activity (84% methyl orange degradation within 300 min) under UV light irradiation. ZnO nanoparticels (NPs) increased the storage modulus of the PZW composite, and the damping factor was transferred to the higher temperature region. The PZW composite exhibited the maximum flexural strength of 58 MPa and a modulus of elasticity (MOE) of 9625 MPa. Meanwhile, it also displayed dimensional stability (thickness swelling value of 9%). PMID:29099777

Evaluation of antibacterial and Antibiofilm activity of Synthesized Zinc-Hydroxyapatite Biocomposites from Labeo rohita fish scale waste

NASA Astrophysics Data System (ADS)

Sathiskumar, Swamiappan; Vanaraj, Sekar; Sabarinathan, Devaraj; Preethi, Kathirvel

2018-02-01

Materials based on hydroxyapatite (HAp) Synthesized from bio-wastes have been regarded as useful, novel, eco-friendly medical applications that are targeted primarily for their antibacterial nature. In the present study, HAp was Synthesized from the fish scales of Labeo rohita using alkaline heat treatment and subsequently mixed with 1, 2 and 3 wt% of zinc (Zn) at 800 °C using calcination method to yield Zn-HAp composites. A detailed characterization of the generated composites was analysed by XRD, FT-IR, SEM, EDX and DLS methods. Further, antibacterial and biofilm inhibitory activity of the generated composites was determined using strains of Staphylococcus aureus and Escherichia coli. The confirmation of the presence of zinc, confirmed by EDAX spectra, XRD, FT-IR, SEM and DLS observations, established that HAp and Zn-HAp composites were without impurities, irregular in shape and were 848 nm sized particles. Although 1-3 wt% Zn-HAp composites showed antibacterial activity, the 3 wt% Zn-HAp composite was found suitable to kill the surrounding bacterial growth and showed potent inhibitory activity against biofilm formation.

Study of Tetrapodal ZnO-PDMS Composites: A Comparison of Fillers Shapes in Stiffness and Hydrophobicity Improvements

PubMed Central

Jin, Xin; Deng, Mao; Kaps, Sören; Zhu, Xinwei; Hölken, Iris; Mess, Kristin; Adelung, Rainer; Mishra, Yogendra Kumar

2014-01-01

ZnO particles of different size and structures were used as fillers to modify the silicone rubber, in order to reveal the effect of the filler shape in the polymer composites. Tetrapodal shaped microparticles, short microfibers/whiskers, and nanosized spherical particles from ZnO have been used as fillers to fabricate the different ZnO-Silicone composites. The detailed microstructures of the fillers as well as synthesized composites using scanning electron microscopy have been presented here. The tensile elastic modulus and water contact angle, which are important parameters for bio-mimetic applications, of fabricated composites with different fillers have been measured and compared. Among all three types of fillers, tetrapodal shaped ZnO microparticles showed the best performance in terms of increase in hydrophobicity of material cross-section as well as the stiffness of the composites. It has been demonstrated that the tetrapodal shaped microparticles gain their advantage due to the special shape, which avoids agglomeration problems as in the case for nanoparticles, and the difficulty of achieving truly random distribution for whisker fillers. PMID:25208080

Study of tetrapodal ZnO-PDMS composites: a comparison of fillers shapes in stiffness and hydrophobicity improvements.

PubMed

Jin, Xin; Deng, Mao; Kaps, Sören; Zhu, Xinwei; Hölken, Iris; Mess, Kristin; Adelung, Rainer; Mishra, Yogendra Kumar

2014-01-01

ZnO particles of different size and structures were used as fillers to modify the silicone rubber, in order to reveal the effect of the filler shape in the polymer composites. Tetrapodal shaped microparticles, short microfibers/whiskers, and nanosized spherical particles from ZnO have been used as fillers to fabricate the different ZnO-Silicone composites. The detailed microstructures of the fillers as well as synthesized composites using scanning electron microscopy have been presented here. The tensile elastic modulus and water contact angle, which are important parameters for bio-mimetic applications, of fabricated composites with different fillers have been measured and compared. Among all three types of fillers, tetrapodal shaped ZnO microparticles showed the best performance in terms of increase in hydrophobicity of material cross-section as well as the stiffness of the composites. It has been demonstrated that the tetrapodal shaped microparticles gain their advantage due to the special shape, which avoids agglomeration problems as in the case for nanoparticles, and the difficulty of achieving truly random distribution for whisker fillers.

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.

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 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.

Superior environment resistance of quartz crystal microbalance with anatase TiO2/ZnO nanorod composite films

NASA Astrophysics Data System (ADS)

Qiang, Wei; Wei, Li; Shaodan, Wang; Yu, Bai

2015-08-01

The precise measurement of quartz crystal microbalance (QCM) in the detection and weighing of organic gas molecules is achieved due to excellent superhydrophobicity of a deposited film composite. Photocatalysis is utilized as a method for the self-cleaning of organic molecules on the QCM for extended long-term stability in the precision of the instrument. In this paper, ZnO nanorod array is prepared via in situ methods on the QCM coated with Au film via hydrothermal process. Subsequently, a TiO2/ZnO composite film is synthesized by surface modification with TiO2 via sol-gel methods. Results show the anatase TiO2/ZnO nanorod composite film with a sharp, pencil-like structure exhibiting excellent superhydrophobicity (water contact angle of 155°), non-sticking water properties, and an autonomous cleaning property under UV irradiation. The anatase TiO2/ZnO nanorod composite film facilitates the precise measurement and extended lifetime of the QCM for the detection of organic gas molecules.

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

Nagpure, I. M., E-mail: indrajitnagpure@gmail.com; Painuly, Deepshikha; Rabanal, Maria Eugenia

The various composition of ZnAlQ{sub 5} such as Zn{sub 1.5}A{sub 10.5}Q{sub 5}, Zn{sub 1}Al{sub 1}Q{sub 5}, Zn{sub 0.5}Al{sub 1.5}Q{sub 5} organic phosphors were prepared via simple cost effective co-precipitation method. The FTIR, SEM, photoluminescence analysis of the prepared phosphors were reported. ZnQ{sub 2} and AlQ{sub 3} were also prepared by similar method and their properties were compared with different composition of ZnAlQ{sub 5}. The structural elucidation in the form of stretching frequencies of chemical bonds of the prepared phosphor was carried out using Fourier Transform Infrared Spectroscopy (FTIR). The stretching frequency analysis confirms the formation of prepared phosphor materials. Themore » SEM analysis shows the surface morphological behavior of prepared phosphor materials. Greenish photoluminescence were observed at 505 to 510 nm for the different composition of ZnAlQ{sub 5},in which Zn{sub 1.5}Al{sub 0.5}Q{sub 5} shows maximum luminescence intensity at 505 nm. PL emission of ZnQ{sub 2} was observed at 515 nm, while for AlQ{sub 3} at 520 nm. The blue shift of 10 nm was observed in Zn{sub 1.5}A{sub 10.5}Q{sub 5} due to modification of energy level due to presence of Zn{sup 2+} and Al{sup 3+}. The enhancement in PL intensity was observed in Zn{sub 1.5}A{sub 10.5}Q{sub 5} compared to the other composition due to transfer of energy between Zn{sup 2+} and quinolate complex. Optical properties of the prepared materials were evaluated for possible applications in organic light emitting devices (OLED).« less

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.

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.

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.

Platinum-free catalysts for low temperature fuel cells

NASA Astrophysics Data System (ADS)

Lastovina, Tatiana; Pimonova, Julia; Budnyk, Andriy

2017-04-01

In this work, we have successfully prepared Zn/Co-N/C and Zn/Co-Fe/N/C composites, both derived from single zeolitic imidazolate framework (ZIF) precursor Zn/Co-ZIF containing equivalent quantities of Zn and Co metal sites. The composites were formed by pyrolysis of the precursor at 700 °C in inert gas atmosphere as such and after mixing it with Fe(II) salt and 1,10-phenontraline in ethanol. Catalytic tests for oxygen reduction reaction (ORR) in electrochemical cell demonstrated promising results allowing us to consider these composites as potential Pt-free catalysts for low temperature fuel cells.

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.

Low cost fabrication of polymer composite (h-ZnO + PDMS) material for piezoelectric device application

NASA Astrophysics Data System (ADS)

Singh, Akanksha; Das, Sonatan; Bharathkumar, Mareddi; Revanth, D.; Karthik, ARB; Sudhakara Sastry, Bala; Ramgopal Rao, V.

2016-07-01

Flexible piezoelectric composites offer alternative and/or additional solutions to sensor, actuator and transducer applications. Here in this work, we have successfully fabricated highly flexible piezoelectric composites with poly dimethyl siloxane (PDMS) using herbal zinc oxide (h-ZnO) as filler having weight fractions up to 50 wt.% by solution casting of dispersions of h-ZnO in PDMS. Excellent piezo properties (Resonant frequency 935 Hz, d*33 29.76 pm V-1), physiochemical properties (Wurtzite structure ZnO, 380 nm absorbance) and mechanical properties (Young modulus 16.9 MPa) have been optimized with theoretical simulations and observed experimentally for h-ZnO + PDMS. As such, the demonstrated piezoelectric PDMS membranes combined with the excellent properties of these composites open new ways to ‘soft touch’ applications and could serve as a variety of soft and sensitive electromechanical transducers, which are desired for a variety of sensor and energy harvesting applications.

Metallic elements and isotope of Pb in wet precipitation in urban area, South America

NASA Astrophysics Data System (ADS)

Migliavacca, Daniela Montanari; Teixeira, Elba Calesso; Gervasoni, Fernanda; Conceição, Rommulo Vieira; Raya Rodriguez, Maria Teresa

2012-04-01

The atmosphere of urban areas has been the subject of many studies to show the atmospheric pollution in large urban centers. By quantifying wet precipitation through the analysis of metallic elements (ICP/AES) and Pb isotopes, the wet precipitation of the Metropolitan Area of the Porto Alegre (MAPA), Brazil, was characterized. The samples were collected between July 2005 and December 2007. Zn, Fe and Mn showed the highest concentration in studied sites. Sapucaia do Sul showed the highest average for Zn, due to influence by the steel plant located near the sampling site. The contribution of anthropogenic emissions from vehicular activity and steel plants in wet precipitation and suspended particulate matter in the MAPA was identified by the isotopic signatures of 208Pb/207Pb and 206Pb/207Pb. Moreover the analyses of the metallic elements allowed also to identify the contribution of other anthropic sources, such as steel plants and oil refinery.

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.

Synthesis of Carbon-Coated ZnO Composite and Varistor Properties Study

NASA Astrophysics Data System (ADS)

Sun, Wei-Jie; Liu, Jin-Ran; Yao, Da-Chuan; Chen, Yong; Wang, Mao-Hua

2017-03-01

In this article, monodisperse ZnO composite nanoparticles were successfully prepared by sol-gel mixed precursor method. Subsequently, carbon as the shell was homogeneously coated on the surface of the ZnO composite nanoparticles via a simple adsorption and calcination process. Microstructural studies of the as-obtained powders were carried out using the techniques of the x-ray powder diffraction, scanning electron microscopy, field emission scanning electron microscopy, transmission electron microscopy with energy dispersive x-ray spectroscopy, and Fourier transform infrared spectroscopy. The results show that the pink ZnO composite powders were fully coated by carbon. Based on the results, the effect of glucose content on the microstructure of the synthesized composites and the electrical properties of the ZnO varistors sintered in air at 1150°C for 2 h were also fully studied. As the amount of glucose increased, the thickness of carbon can be increased from 2.5 nm to 5 nm. In particular, the ZnO varistor fabricated with the appropriate thickness of the carbon coating (5 nm) leads to the superior electrical performance, with present high breakdown voltage ( V b = 420 V/mm) and excellent nonlinear coefficient ( α = 61.7), compared with the varistors obtained without carbon coating.

Synthesis of ZnFe2O4/SiO2 composites derived from a diatomite template.

PubMed

Liu, Zhaoting; Fan, Tongxiang; Zhou, Han; Zhang, Di; Gong, Xiaolu; Guo, Qixin; Ogawa, Hiroshi

2007-03-01

A novel porous ZnFe2O4/SiO2 composite product has been generated with a template-directed assembly method from porous diatomite under different synthesis conditions, such as precursor concentrations (metallic nitrates), calcination temperature and diatomite type. The phase composition and morphology of all the materials were examined by x-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). The results indicated that an inherited hierarchical porous structure from the diatomite template can be obtained, and the synthesis conditions were found to have clear effects on the formation of the ZnFe2O4/SiO2 composite. The ideal composite of ZnFe2O4/SiO2 can be obtained through optimization of diatomite template type, precursor solution and calcination temperature. Furthermore, the adsorption abilities of two types of diatomites were analyzed in detail using FTIR spectra and nitrogen adsorption measurements etc, which proved that A-diatomite (Shengzhou-diatomite) is better than B-diatomite (Changbai-diatomite) on the aspect of adsorbing Zn and Fe ions, and of forming the ZnFe2O4.

Growth of amorphous and epitaxial ZnSiP 2–Si alloys on Si

DOE PAGES

Martinez, Aaron D.; Miller, Elisa M.; Norman, Andrew G.; ...

2018-01-30

ZnSiP 2is a wide band gap material lattice matched with Si, with potential for Si-based optoelectronics. Here, amorphous ZnSiP 2–Si alloys are grown with tunable composition. Films with Si-rich compositions can be crystallized into epitaxial films.

Metamorphic ore remobilization in the Hällefors district, Bergslagen, Sweden: constraints from mineralogical and small-scale sulphur isotope studies

NASA Astrophysics Data System (ADS)

Wagner, Thomas; Jonsson, Erik; Boyce, Adrian J.

2005-07-01

The marble- and metavolcanic-hosted Pb Zn (Ag Sb As) deposits of the Hällefors district, located in the Palaeoproterozoic Bergslagen ore province, south central Sweden, comprise both stratabound sulphides and discordant, Ag-rich sulphide sulphosalt veins. The complex sulphide sulphosalt assemblages of the Alfrida-Jan Olof mines at Hällefors were investigated by a combination of ore microscopy, electron-microprobe analysis, and in situ laser sulphur isotope analysis. The massive ore is characterized by positive and homogeneous δ34S (+1.4‰ to +2.7‰ V-CDT), whereas vein-hosted sulphides and sulphosalts exhibit similar, but generally less positive to slightly negative δ34S (-0.6‰ to +2.0‰). Comparison of the observed ore mineral assemblages with calculated phase equilibria in the system Fe As S O H and isotopic fractionation as a function of temperature, oxygen fugacity and pH indicates that the vein-type mineralization was formed from relatively reduced and rather alkaline hydrothermal fluids. At these reduced conditions, fractionation of δ34S via changes of fO2 is insignificant, and thus the isotopic signatures of the vein minerals directly reflect the composition of the sulphur source. We therefore conclude that the vein-type ore essentially inherited the sulphur isotope signature from the pre-existing massive sulphides via metamorphic remobilization at approximately 300 400°C and 2 3 kbar. Scales of remobilization observable are on the order of about 5 mm to 30 cm. Overall, the sulphide sulphosalt assemblages from the Alfrida-Jan Olof mines exhibit δ34S values which are comparable to a majority of metasupracrustal-hosted deposits in the Bergslagen province, thereby suggesting a common origin from ca. 1.90 1.88 Ga volcanic-hydrothermal processes.

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

Low temperature magnetization and anomalous high temperature dielectric behaviour of (1-x) YMnO3/xZnFe2O4 composites

NASA Astrophysics Data System (ADS)

Kumar, Virendra; Gaur, Anurag

2018-04-01

We synthesized YMnO3 and ZnFe2O4 composites, (1-x)YMnO3/x(ZnFe2O4) with x = 0, 0.05, 0.10, and 0.15 by high temperature sintering. X-ray diffraction (XRD) patterns indicate the successful formation of composites. Weak ferromagnetism is manifested below Néel temperature (TN) for pristine YMnO3, according to (M-H) study performed at 10 K. For (1-x)YMnO3/xZnFe2O4 (x = 0.05, 0.10, 0.15) a thin coercivity is observed in all compositions, due to short range magnetic ordering at low temperature after the insertion of ZnFe2O4. For pristine YMnO3 explicit divarication between FC-ZFC curves is observed, with crimps observed in both FC and ZFC curves at 75 K, which is the TN of YMnO3. For 1-x(YMnO3)/x ZnFe2O4 composites (x = 0.05, 0.10, 0.15) crimps are perceived only in ZFC curves at slightly varying values of 39.8, 42.32 and 45.63 K respectively. Anomalous peaks are observed in high temperature dielectric curves above 400 K for 1-x(YMnO3)/xZnFe2O4 (x = 0, 0.05, 0.10, 0.15) composites due to Maxwell-Wagner relaxation effect.

Synthesis of SiO2-Coated Core-Shell ZnO Composites for Preparing High-Voltage Varistors

NASA Astrophysics Data System (ADS)

Qu, Xiao; Yao, Da-Chuan; Liu, Jin-Ran; Wang, Mao-Hua; Zhang, Han-Ping

2018-01-01

Monodispersed ZnO composite microspheres were successfully prepared by a facile ultrasound irradiation method. Then, the uniform core-shell structured composites were synthesized through the hydrolysis of tetraethyl orthosilicate on the surface of the ZnO composite microspheres. Microstructural studies of the as-obtained powders were carried out using the techniques of the x-ray powder diffraction, field emission scanning electron microscopy and transmission electron microscopy with energy dispersive x-ray spectroscopy. The results show that the pink ZnO composite powders as the core were spherical structures with the size of approximately 100 nm, and the SiO2 shell was fully coated on the surface of the core. On the basis of these results, the effect of SiO2 content on the thickness of the synthesized composites and microstructure, as well as the electrical properties of the ZnO varistors sintered in air at 1150°C for 2 h, were fully studied. In particular, the ZnO varistor prepared with the appropriate amount of the SiO2 coating (˜40 nm) leads to a superior electrical performance with the high breakdown voltage of 418 V mm-1 and an excellent nonlinear coefficient of 70.7, compared with the varistors obtained without the SiO2 coating. The high performance is attributed to the smaller and more homogeneous ZnO grains obtained via the SiO2 coating.

Iron Bioavailability from Ferric Pyrophosphate in Extruded Rice Cofortified with Zinc Sulfate Is Greater than When Cofortified with Zinc Oxide in a Human Stable Isotope Study.

PubMed

Hackl, Laura; Zimmermann, Michael B; Zeder, Christophe; Parker, Megan; Johns, Paul W; Hurrell, Richard F; Moretti, Diego

2017-03-01

Background: Extruded rice grains are often cofortified with iron and zinc. However, it is uncertain if the addition of zinc to iron-fortified rice affects iron absorption and whether this is zinc-compound specific. Objective: We investigated whether zinc, added as zinc oxide (ZnO) or zinc sulfate (ZnSO 4 ), affects human iron absorption from extruded rice fortified with ferric pyrophosphate (FePP). Methods: In 19 iron-depleted Swiss women (plasma ferritin ≤16.5 μ/L) aged between 20 and 39 y with a normal body mass index (in kg/m 2 ; 18.7-24.8), we compared iron absorption from 4 meals containing fortified extruded rice with 4 mg Fe and 3 mg Zn. Three of the meals contained extruded rice labeled with FePP ( 57 FePP): 1 ) 1 meal without added zinc ( 57 FePP-Zn), 2 ) 1 cofortified with ZnO ( 57 FePP+ZnO), and 3 ) 1 cofortified with ZnSO 4 ( 57 FePP+ZnSO 4 ). The fourth meal contained extruded rice without iron or zinc, extrinsically labeled with ferrous sulfate ( 58 FeSO 4 ) added as a solution after cooking. All 4 meals contained citric acid. Iron bioavailability was measured by isotopic iron ratios in red blood cells. We also measured relative in vitro iron solubility from 57 FePP-Zn, 57 FePP+ZnO, and 57 FePP+ZnSO 4 expressed as a fraction of FeSO 4 solubility. Results: Geometric mean fractional iron absorption (95% CI) from 57 FePP+ZnSO 4 was 4.5% (3.4%, 5.8%) and differed from 57 FePP+ZnO (2.7%; 1.8%, 4.1%) ( P < 0.03); both did not differ from 57 FePP-Zn: 4.0% (2.8%, 5.6%). Relative iron bioavailabilities compared with 58 FeSO 4 were 62%, 57%, and 38% from 57 FePP+ZnSO 4 , 57 FePP-Zn, and 57 FePP+ZnO, respectively. In vitro solubility from 57 FePP+ZnSO 4 differed from that of 57 FePP-Zn (14.3%; P < 0.02) but not from that of 57 FePP+ZnO (10.2% compared with 13.1%; P = 0.08). Conclusions: In iron-depleted women, iron absorption from FePP-fortified extruded rice cofortified with ZnSO 4 was 1.6-fold (95% CI: 1.4-, 1.9-fold) that of rice cofortified with ZnO. These findings suggest that ZnSO 4 may be the preferable zinc cofortificant for optimal iron bioavailability of iron-fortified extruded rice. This trial was registered at clinicaltrials.gov as NCT02255942. © 2017 American Society for Nutrition.

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.

Optical, electrical properties and structural characterization of ZnO:rGO based photodetector

NASA Astrophysics Data System (ADS)

Nath, Debarati; Mandal, S. K.; Deb, Debajit; Rakshit, J. K.; Dey, P.; Roy, J. N.

2018-04-01

Pure ZnO and ZnO:rGO composite films are prepared by sol-gel process and the effect of reduced graphene oxide(rGO) on structural, optical and electrical properties of the film are studied. UV-visspectrum shows that composite film exhibit similar optical absorbance property as pure ZnOfilm. Band gap of the film is changed from 3.32 to 3.21 eV by incorporation of rGO. From current-voltage curve it can be observed that photo current is increased significantly in composite film under red laser light illumination. This result suggests that conduction mechanism in composite film is dominated by rGO. Nyquist plot of both films show only one semicircle behavior in measured frequency range, which may be attributed to grain boundaries effects in the composite.

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.

The Design of Dual-Emissive Composite Material [Zn2(HL)3]+@MOF-5 as Self-Calibrating Luminescent Sensors of Al3+ Ions and Monoethanolamine.

PubMed

Wu, Meng-Meng; Wang, Jiao-Yang; Sun, Rui; Zhao, Cui; Zhao, Jiong-Peng; Che, Guang-Bo; Liu, Fu-Chen

2017-08-21

Introducing another chromophore into a luminescent MOF is a potential way to assembling novel dual-emissive luminescent materials. Putting the chromophore, for which luminescence can be enhanced by Zn 2+ ion, into MOF-5 by the "bottle around ship" strategy is a simple but efficient synthesis method to realize such dual-emissive materials. According to this strategy, a novel dual-emissive luminescent composite material [Zn 2 (HL) 3 ] + @MOF-5 was constructed by loading the [La 3 (HL) 2 L 2 (NO 3 ) 3 H 2 O] (1) (H 2 L = 7,7'-(ethane-1,1'-diyl)8-hydro-quinoline) into MOF-5, in which the [Zn 2 (HL) 3 ] + anions were transformed from 1 with the existence of Zn 2+ . The dual-emissive composite materials show excellent luminescence with two emissions of MOF-5 at 410 nm and [Zn 2 (HL) 3 ] + at 524 nm. Furthermore, by combining characteristics of MOF-5 and the guest chromophore, the composite material is highly selectively sensitive toward Al 3+ and monoethanolamine, which makes [Zn 2 (HL) 3 ] + @MOF-5 a potential self-calibrated fluorescence sensor.

Synthesis of TiO2 NRs - ZnO Composite for Dye Sensitized Solar Cell Photoanodes

NASA Astrophysics Data System (ADS)

Wahyuningsih, S.; Ramelan, A. H.; Hidayat, R.; Fadillah, G.; Munawaroh, H.; Saputri, L. N. M. Z.

2017-07-01

Composite of TiO2 NRs - ZnO were synthesized for DSSCs photoanode materials. TiO2 NRs was synthesized from TiO2 anatase by mechanochemical technique using ball milling process with agitation speed of 1000 rpm. While, the further hydrothermal refluxing process was conducted at 120°C under various concentration of NaOH in aqueous solution. The starting material of ZnO was prepared from ZnSO4.7H2O as a precursor. The hydrothermal treated TiO2 was added to the ZnO powder in a certain composition of 1:1, 1:2 and 2:1 (w/w), and the mixtures were then annealed at 400°C. The resulting material was characterized by X-ray diffraction (XRD), Surface area analyzer (SAA), Transmission electron microscopy (TEM), and Thermogravimetry/Differential thermal analysis (TG/DTA). The TiO2 revolution occurs from anatase phase into brookite phase. Rutile TiO2 phase was increasing when the NaOH was added at about 12 M. Nanograf of TEM showed the optimum condition for the formation of TiO2 NRs was obtained when 12 M NaOH was used. Structural transformation to 1D nanorods of TiO2 capable increase surface area up to 79 m2/g. TiO2 NRs-ZnO composite was prepared from TiO2 NRs and ZnO using comparation of TiO2 NRs: ZnO = 1:1, 1:2, dan 2:1. Anatase phase TiO2 as a single phase TiO2 was obtained in the TiO2-ZnO composite (1:1 w/w) upon heating the sample until 400°C. Difference TiO2 NRs-ZnO composite materials were investigated as good photovoltaic materials. Evaluation of the performance of DSSCs was conducted by I-V Keithley 2602A measurement indicate that photoanode built of TiO2 NRs - ZnO thin film has a higher solar cell efficiency than that of TiO2 thin film photoanode.

Development of silver and zinc oxide decorated nanoclay containing polymeric composites for water disinfection applications

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

Motshekga, Sarah C.; Department of Chemical, Metallurgical and Materials Engineering, Tshwane University of Technology, Pretoria, 0001; Ray, Suprakas Sinha

Contaminated drinking water has serious implications to the human health that could lead to death. The rapid growth of bacterial contamination in drinking water is alarming, and yet a robust and cost effective method with less limitation has not been developed. The current study is aimed at evaluating the performance of nanoclay composites dispersed in chitosan biopolymer as an antibacterial material. The performances of the composites were evaluated using the batch kinetic studies. Three composites of Ag-CtsB, ZnO-CtsB and Ag/ZnO-CtsB were prepared and evaluated against gram negative Escherichia coli and gram positive Enterococcus faecalis bacteria. The composites were characterized bymore » powder X-ray diffraction, scanning electron microscope, energy dispersive spectroscopy and BET surface area measurements. Antibacterial activity results showed that the composites can be a potent bactericide material for water disinfection as they are highly effective against both gram negative and gram positive bacteria tested. Whereas both Ag-CtsB and ZnO-CtsB composites showed good antibacterial activity against bacteria with removal efficiency from 51%, best antibacterial activity was observed with Ag/ZnO-CtsB composite with removal efficiency from 78%. The results revealed that Ag/ZnO-CtsB composite is a promising bactericide that is highly effective against both gram negative and gram positive bacteria tested.« less

Development of silver and zinc oxide decorated nanoclay containing polymeric composites for water disinfection applications

NASA Astrophysics Data System (ADS)

Motshekga, Sarah C.; Ray, Suprakas Sinha; Onyango, Maurice S.; Momba, Maggie N. B.

2015-05-01

Contaminated drinking water has serious implications to the human health that could lead to death. The rapid growth of bacterial contamination in drinking water is alarming, and yet a robust and cost effective method with less limitation has not been developed. The current study is aimed at evaluating the performance of nanoclay composites dispersed in chitosan biopolymer as an antibacterial material. The performances of the composites were evaluated using the batch kinetic studies. Three composites of Ag-CtsB, ZnO-CtsB and Ag/ZnO-CtsB were prepared and evaluated against gram negative Escherichia coli and gram positive Enterococcus faecalis bacteria. The composites were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive spectroscopy and BET surface area measurements. Antibacterial activity results showed that the composites can be a potent bactericide material for water disinfection as they are highly effective against both gram negative and gram positive bacteria tested. Whereas both Ag-CtsB and ZnO-CtsB composites showed good antibacterial activity against bacteria with removal efficiency from 51%, best antibacterial activity was observed with Ag/ZnO-CtsB composite with removal efficiency from 78%. The results revealed that Ag/ZnO-CtsB composite is a promising bactericide that is highly effective against both gram negative and gram positive bacteria tested.

Impact of metal matrix composite on the evolution and erosion performance characteristics of non lubricated-dry abrasive degradation of ternary composite coating for refineries system

NASA Astrophysics Data System (ADS)

Anawe, Paul Apeye Lucky; Fayomi, Ojo Sunday Isaac

2018-06-01

The application of rational design principles and process in electrodeposition can eliminate many engineering catastrophes related to corrosion and micromechanical failure in service. This has led to appreciate the need of surface modification on component for enhance life span. Admixed Zn-30Al-13Ti-chloride composite bath was electrolytically prepared and successfully deposited on UNS G10150 mild steel substrate by zinc dual anode deposition processes within an interval of applied current density, particle concentration and constant time. The codeposition of Zn-Al-Ti coating was studied in the presence of other bath ingredient. The effect of deposition current and particle concentration on structural property, adhesion behaviour, ideal crystal orientation, surface topography and electrochemical properties of Zn-Al-Ti alloy coating series on mild steel were analytically examined. The wear stability of the developed composite materials was examined via sliding reciprocating rig. The structural integrity was examined with scanning electron microscope equipped with EDS, X-ray diffraction; Atomic force microscope, dura scan micro-hardness tester and 3 μ metrohm Potentiostat/galvanostat. Interestingly the induced activity of the Zn-Al-Ti chloride composite alloy results into excellent structural modification and stable crystal precipitation within the structural interface as a result of Zn3Al, Zn2Ti and ZnAl3Ti2 intermetallic phase. The obtained results showed that the introduction of Ti particles in the presence of other bath additive in the plating bath mostly modified the surface and brings an increase in the microhardness, corrosion resistance and reduce wear deformation of Zn-Al-Ti chloride composite alloy.

Genesis of the Bangbule Pb-Zn-Cu polymetallic deposit in Tibet, western China: Evidence from zircon U-Pb geochronology and S-Pb isotopes

NASA Astrophysics Data System (ADS)

Kan, Tian; Zheng, Youye; Gao, Shunbao

2016-04-01

The Banbule Pb-Zn-Cu skarn deposit is located in the Longger-Gongbujiangda volcanic magma arc in the Gangdese-Nyainqentanglha Plate. It is the only lead-zinc polymetallic deposit discovered in the westernmost Nyainqentanglha metallogenic belt. The measured and indicated resources include 0.9 Mt of Pb+Zn (4.77% Pb and 4.74% Zn, respectively), 6499 t of Cu, and 178 t of Ag (18.75g/t Ag). The orebodies mainly occur as lenses, veins and irregular shapes in the contact zone between the quartz-porphyry and limestone of the Upper Permian Xiala Formation, or in the boundaries between limestone and sandstone. Pb-Zn-Cu mineralization in the Banbule deposit is closely associated with skarns. The ore minerals are dominated by galena, sphalerite, chalcopyrite, bornite, and magnetite, with subordinate pyrite, malachite, and azurite. The gangue minerals are mainly garnet, actinolite, diopside, quartz, and calcite. The ore-related quartz-porphyry displays LA-ICP-MS zircon U-Pb age of 77.31±0.74 Ma. The δ34S values of sulfides define a narrow range of -0.8 to 4.7‰ indicating a magmatic source for the ore-forming materials. Lead isotopic systematics yield 206Pb/204Pb of 18.698 to 18.752, 207Pb/204Pb of 15.696 to 15.760, and 208Pb/204Pb of 39.097 to 39.320. The data points are constrained around the growth curves of upper crust and orogenic belt according to the tectonic discrimination diagrams. The calculated Δβ - Δγ values plot within the magmatic field according to the discrimination diagram of Zhu et al. (1995). The S-Pb isotopic data suggest that Bangbule is a typical skarn deposit, and the Pb-Zn-Cu mineralization is genetically related to the quartz-porphyry in the mining district. The discovery of the Bangbule deposit indicates that there is metallogenic potential in the westernmost Nyainqentanglha belt, which is of great importance for the exploration work in this area.

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

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.

Corrosion resistance of Zn-Al layered double hydroxide/poly(lactic acid) composite coating on magnesium alloy AZ31

NASA Astrophysics Data System (ADS)

Zeng, Rong-Chang; Li, Xiao-Ting; Liu, Zhen-Guo; Zhang, Fen; Li, Shuo-Qi; Cui, Hong-Zhi

2015-12-01

A Zn-Al layered double hydroxide (ZnAl-LDH) coating consisted of uniform hexagonal nano-plates was firstly synthesized by co-precipitation and hydrothermal treatment on the AZ31 alloy, and then a poly(lactic acid) (PLA) coating was sealed on the top layer of the ZnAl-LDH coating using vacuum freeze-drying. The characteristics of the ZnAl-LDH/PLA composite coatings were investigated by means of XRD, SEM, FTIR and EDS. The corrosion resistance of the coatings was assessed by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results showed that the ZnAl-LDH coating contained a compact inner layer and a porous outer layer, and the PLA coating with a strong adhesion to the porous outer layer can prolong the service life of the ZnAl-LDH coating. The excellent corrosion resistance of this composite coating can be attributable to its barrier function, ion-exchange and self-healing ability.

Room-temperature wide-range luminescence and structural, optical, and electrical properties of SILAR deposited Cu-Zn-S nano-structured thin films

NASA Astrophysics Data System (ADS)

Jose, Edwin; Kumar, M. C. Santhosh

2016-09-01

We report the deposition of nanostructured Cu-Zn-S composite thin films by Successive Ionic Layer Adsorption and Reaction (SILAR) method on glass substrates at room temperature. The structural, morphological, optical, photoluminescence and electrical properties of Cu-Zn-S thin films are investigated. The results of X-ray diffraction (XRD) and Raman spectroscopy studies indicate that the films exhibit a ternary Cu-Zn-S structure rather than the Cu xS and ZnS binary composite. Scanning electron microscope (SEM) studies show that the Cu-Zn-S films are covered well over glass substrates. The optical band gap energies of the Cu-Zn-S films are calculated using UV-visible absorption measurements, which are found in the range of 2.2 to 2.32 eV. The room temperature photoluminescence studies show a wide range of emissions from 410 nm to 565 nm. These emissions are mainly due to defects and vacancies in the composite system. The electrical studies using Hall effect measurements show that the Cu-Zn-S films are having p-type conductivity.

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.

Surface compositions of atomic layer deposited Zn{sub 1−x}Mg{sub x}O thin films studied using Auger electron spectroscopy

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

Xie, Ting; Romero, Danilo; Gomez, Romel D., E-mail: rdgomez@umd.edu

2015-09-15

In this paper, the authors present Auger electron spectroscopy (AES) studies of Zn{sub 1−x}Mg{sub x}O (ZMO) films grown via interrupted atomic-layer deposition (ALD) techniques. The ZMO films were fabricated by alternating ALD deposition of ZnO and MgO layers up to 1000 cycles. Zn{sub 1−x}Mg{sub x}O films with progressively decreasing Mg/Zn ratios (Mg/Zn = 1/1, 1/2, 1/3, 1/4, 1/5, 1/6, 1/9, and 2/8, 3/12, 4/16, and 5/20) were fabricated for this study. The AES results exhibit an abrupt drop of Mg composition on the ZMO surface when the Mg/Zn < 1/3. Additionally, the surface composition ratios of O to Mg, O to Zn, and Mgmore » to Zn were estimated with known Auger sensitivity factors. The results indicate that Mg ions diffuse into the bulk, forming Zn{sub 1−x}Mg{sub x}O alloys.« less

Uniform Fe3O4 coating on flower-like ZnO nanostructures by atomic layer deposition for electromagnetic wave absorption.

PubMed

Wan, Gengping; Wang, Guizhen; Huang, Xianqin; Zhao, Haonan; Li, Xinyue; Wang, Kan; Yu, Lei; Peng, Xiange; Qin, Yong

2015-11-21

An elegant atomic layer deposition (ALD) method has been employed for controllable preparation of a uniform Fe3O4-coated ZnO (ZnO@Fe3O4) core-shell flower-like nanostructure. The Fe3O4 coating thickness of the ZnO@Fe3O4 nanostructure can be tuned by varying the cycle number of ALD Fe2O3. When serving as additives for microwave absorption, the ZnO@Fe3O4-paraffin composites exhibit a higher absorption capacity than the ZnO-paraffin composites. For ZnO@500-Fe3O4, the effective absorption bandwidth below -10 dB can reach 5.2 GHz and the RL values below -20 dB also cover a wide frequency range of 11.6-14.2 GHz when the coating thickness is 2.3 mm, suggesting its potential application in the treatment of the electromagnetic pollution problem. On the basis of experimental observations, a mechanism has been proposed to understand the enhanced microwave absorption properties of the ZnO@Fe3O4 composites.

Manipulation of ZnO composition affecting electrical properties of MEH-PPV: ZnO nanocomposite thin film via spin coating for OLEDs application

NASA Astrophysics Data System (ADS)

Azhar, N. E. A.; Shariffudin, S. S.; Alrokayan, Salman A. H.; Khan, Haseeb A.; Rusop, M.

2018-05-01

Recent investigations of the promising materials for optoelectronic have been demonstrated by introducing n-type inorganic material into conjugated polymer. Morphology, optical and electrical of nanocomposites thin films based on poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) and zinc oxide (ZnO) nanotetrapods with various ZnO composition (0 wt% to 0.4 wt%) have been investigated. The MEH-PPV: ZnO nanocomposite thin film was deposited using spin-coating method. Surface morphology was characterized using field emission scanning electron microscopy and shows the uniform dispersion of MEH-PPV and ZnO phases for sample deposited at 0.2 wt%. The photoluminescence (PL) spectra shows the visible emission intensities increased when the ZnO composition increased. The current-voltage (I-V) measurement shows the highest conductivity of nanocomposite thin film deposited at 0.2 wt% of ZnO is 7.40 × 10-1 S. cm-1. This study will provide better performance and suitable for optoelectronic device especially OLEDs application.

Acetone gas sensor based on NiO/ZnO hollow spheres: Fast response and recovery, and low (ppb) detection limit.

PubMed

Liu, Chang; Zhao, Liupeng; Wang, Boqun; Sun, Peng; Wang, Qingji; Gao, Yuan; Liang, Xishuang; Zhang, Tong; Lu, Geyu

2017-06-01

NiO/ZnO composites were synthesized by decorating numerous NiO nanoparticles on the surfaces of well dispersed ZnO hollow spheres using a facile solvothermal method. Various kinds of characterization methods were utilized to investigate the structures and morphologies of the hybrid materials. The results revealed that the NiO nanoparticles with a size of ∼10nm were successfully distributed on the surfaces of ZnO hollow spheres in a discrete manner. As expected, the NiO/ZnO composites demonstrated dramatic improvements in sensing performances compared with pure ZnO hollow spheres. For example, the response of NiO/ZnO composites to 100ppm acetone was ∼29.8, which was nearly 4.6 times higher than that of primary ZnO at 275°C, and the response/recovery time were 1/20s, respectively. Meanwhile, the detection limit could extend down to ppb level. The likely reason for the improved gas sensing properties was also proposed. Copyright © 2017 Elsevier Inc. All rights reserved.

Shell evolution beyond Z = 28 and N = 50: Spectroscopy of 81,82,83,84Zn

NASA Astrophysics Data System (ADS)

Shand, C. M.; Podolyák, Zs.; Górska, M.; Doornenbal, P.; Obertelli, A.; Nowacki, F.; Otsuka, T.; Sieja, K.; Tostevin, J. A.; Tsunoda, Y.; Authelet, G.; Baba, H.; Calvet, D.; Château, A.; Chen, S.; Corsi, A.; Delbart, A.; Gheller, J. M.; Giganon, A.; Gillibert, A.; Isobe, T.; Lapoux, V.; Matsushita, M.; Momiyama, S.; Motobayashi, T.; Niikura, M.; Otsu, H.; Paul, N.; Péron, C.; Peyaud, A.; Pollacco, E. C.; Roussé, J.-Y.; Sakurai, H.; Santamaria, C.; Sasano, M.; Shiga, Y.; Steppenbeck, D.; Takeuchi, S.; Taniuchi, R.; Uesaka, T.; Wang, H.; Yoneda, K.; Ando, T.; Arici, T.; Blazhev, A.; Browne, F.; Bruce, A. M.; Carroll, R. J.; Chung, L. X.; Cortés, M. L.; Dewald, M.; Ding, B.; Dombrádi, Zs.; Flavigny, F.; Franchoo, S.; Giacoppo, F.; Gottardo, A.; Hadyńska-Klęk, K.; Jungclaus, A.; Korkulu, Z.; Koyama, S.; Kubota, Y.; Lee, J.; Lettmann, M.; Linh, B. D.; Liu, J.; Liu, Z.; Lizarazo, C.; Louchart, C.; Lozeva, R.; Matsui, K.; Miyazaki, T.; Moschner, K.; Nagamine, M.; Nakatsuka, N.; Nishimura, S.; Nita, C. R.; Nobs, C. R.; Olivier, L.; Ota, S.; Orlandi, R.; Patel, Z.; Regan, P. H.; Rudigier, M.; Şahin, E.; Saito, T.; Söderström, P.-A.; Stefan, I.; Sumikama, T.; Suzuki, D.; Vajta, Zs.; Vaquero, V.; Werner, V.; Wimmer, K.; Wu, J.; Xu, Z. Y.

2017-10-01

We report on the measurement of new low-lying states in the neutron-rich 81,82,83,84Zn nuclei via in-beam γ-ray spectroscopy. These include the 41+ → 21+ transition in 82Zn, the 21+ → 0g.s.+ and 41+ → 21+ transitions in 84Zn, and low-lying states in 81,83Zn were observed for the first time. The reduced E ( 21+) energies and increased E (41+) / E (2+1) ratios at N = 52, 54 compared to those in 80Zn attest that the magicity is confined to the neutron number N = 50 only. The deduced level schemes are compared to three state-of-the-art shell model calculations and a good agreement is observed with all three calculations. The newly observed 2+ and 4+ levels in 84Zn suggest the onset of deformation towards heavier Zn isotopes, which has been incorporated by taking into account the upper sdg orbitals in the Ni78-II and the PFSDG-U models.

Asymmetric ZnO panel-like hierarchical architectures with highly interconnected pathways for free-electron transport and photovoltaic improvements.

PubMed

Shi, Yantao; Zhu, Chao; Wang, Lin; Li, Wei; Fung, Kwok Kwong; Wang, Ning

2013-01-02

Through a rapid and template-free precipitation approach, we synthesized an asymmetric panel-like ZnO hierarchical architecture (PHA) for photoanodes of dye-sensitized solar cells (DSCs). The two sides of the PHA are constructed differently using densely interconnected, mono-crystalline and ultrathin ZnO nanosheets. By mixing these PHAs with ZnO nanoparticles (NPs), we developed an effective and feasible strategy to improve the electrical transport and photovoltaic performance of the composite photoanodes of DSCs. The highly crystallized and interconnected ZnO nanosheets largely minimized the total grain boundaries within the composite photoanodes and thus served as direct pathways for the transport and effective collection of free electrons. Through low-temperature (200 °C) annealing, these novel composite photoanodes achieved high conversion efficiencies of up to 5.59% for ZnO-based quasi-solid DSCs. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A vanadium-doped ZnO nanosheets-polymer composite for flexible piezoelectric nanogenerators.

PubMed

Shin, Sung-Ho; Kwon, Yang Hyeog; Lee, Min Hyung; Jung, Joo-Yun; Seol, Jae Hun; Nah, Junghyo

2016-01-21

We report high performance flexible piezoelectric nanogenerators (PENGs) by employing vanadium (V)-doped ZnO nanosheets (NSs) and the polydimethylsiloxane (PDMS) composite structure. The V-doped ZnO NSs were synthesized to overcome the inherently low piezoelectric properties of intrinsic ZnO. Ferroelectric phase transition induced in the V-doped ZnO NSs contributed to significantly improve the performance of the PENGs after the poling process. Consequently, the PENGs exhibited high output voltage and current up to ∼32 V and ∼6.2 μA, respectively, under the applied strain, which are sufficient to directly turn on a number of light emitting diodes (LEDs). The composite approach for PENG fabrication is scalable, robust, and reproducible during periodic bending/releasing over extended cycles. The approach introduced here extends the performance limits of ZnO-based PENGs and demonstrates their potential as energy harvesting devices.

Oceanic Pb-isotopic sources of proterozoic and paleozoic volcanogenic massive sulfide deposits on Prince of Wales Island and vicinity, southeastern Alaska

USGS Publications Warehouse

Ayuso, Robert A.; Karl, Susan M.; Slack, John F.; Haeussler, Peter J.; Bittenbender, Peter E.; Wandless, Gregory A.; Colvin, Anna

2005-01-01

Volcanogenic massive sulfide (VMS) deposits on Prince of Wales Island and vicinity in southeastern Alaska are associated with Late Proterozoic through Cambrian volcanosedimentary rocks of the Wales Group and with Ordovician through Early Silurian felsic volcanic rocks of the Moira Sound unit (new informal name). The massive sulfide deposits in the Wales Group include the Big Harbor, Copper City, Corbin, Keete Inlet, Khayyam, Ruby Tuesday, and Stumble-On deposits, and those in the Moira Sound unit include the Barrier Islands, Moira Copper, Niblack, and Nichols Bay deposits. Pb-isotopic signatures were determined on sulfide minerals (galena, pyrite, chalcopyrite, pyrrhotite, and sphalerite) to constrain metal sources of the massive sulfides and for comparison with data for other deposits in the region. Except for the Ruby Tuesday deposit, galena is relatively rare in most of these deposits. Pb-isotopic signatures distinguish the mainly Cu+Zn±Ag±Au massive sulfide deposits in the Wales Group from the Zn+Cu±Ag±Au massive sulfide deposits in the Moira Sound unit. Among the older group of deposits, the Khayyam deposit has the widest variation in Pb-isotopic ratios (206Pb/204Pb=17.169–18.021, 207Pb/204Pb=15.341–15.499, 208Pb/204Pb=36.546–37.817); data for the other massive sulfide deposits in the Wales Group overlap the isotopic variations in the Khayyam deposit. Pb-isotopic ratios for both groups of deposits are lower than those on the average crustal Pbevolution curve (µ=9.74), attesting to a large mantle influence in the Pb source. All the deposits show no evidence for Pb evolution primarily in the upper or lower continental crust. Samples from the younger group of deposits have scattered Pb-isotopic compositions and plot as a broad band on uranogenic and thorogenic Pb diagrams. Data for these deposits overlap the trend for massive sulfide deposits in the Wales Group but extend to significantly more radiogenic Pb-isotopic values. Pb-isotopic ratios of samples from the massive sulfide deposits in the Moira Sound unit plot on a different trend (206Pb/204Pb=17.375–19.418, 207Pb/204Pb=15.361–15.519, 208Pb/204Pb=36.856–37.241) from the steep slope defined by the massive sulfide deposits in the Wales Group. In comparison, the Pb-isotopic ratios of Devonian polymetallic (Pb-Zn-Au-Ag) quartz-sulfide veins vary widely ( 206Pb/204Pb=18.339–18.946, 207Pb/204Pb=15.447–15.561, 208Pb/204Pb=37.358–38.354), straddling the slope defined by the massive sulfide deposits in the Moira Sound unit. The general decrease in 207Pb/204Pb ratio in these deposits, relative to the average crustal Pb-evolution curve, suggests that the most likely lead sources were those associated with oceanic volcanic rocks. The massive sulfide deposits in the Wales Group may have resided within an intraoceanic tectonic setting where the mantle was the predominant contributor of metals. Some contribution from reworked arc material or recycled older, hydrothermally altered oceanic crust (including pelagic sediment) is also possible. Lead sources of the massive sulfide deposits in the Moira Sound unit also included an older source region, possibly a Late Proterozoic or Cambrian volcanosedimentary sequence and the massive sulfide deposits in the Wales Group. Preliminary regional comparison of the Pb-isotopic data indicates that the Greens Creek (Admiralty Island, Alaska) and Windy Craggy (northern British Columbia) deposits probably did not share a common lead source with the VMS deposits on Prince of Wales Island. Other sulfide occurrences on Admiralty Island are also more radiogenic than those on Prince of Wales Island. Large differences in 207Pb/204Pb ratio suggest that the lead in the VMS deposits in different parts of the Alexander terrane evolved from sources with heterogeneous U/Pb ratios, resulting from mixing of mantle and crustal components. 

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.

The Preparation, Characterization, Mechanical and Antibacterial Properties of GO-ZnO Nanocomposites with a Poly(l-lactide)-Modified Surface

PubMed Central

Yuan, Mingwei; Xiong, Chengdong; Jiang, Lin; Li, Hongli

2018-01-01

Graphene oxide (GO) was employed for the preparation of GO-zinc oxide (ZnO). The hydroxyl group on the surface was exploited to trigger the l-lactide ring-opening polymerization. A composite material with poly(l-lactide) (PLLA) chains grafted to the GO-ZnO surface, GO-ZnO-PLLA, was prepared. The results demonstrated that the employed method allowed one-step, rapid grafting of PLLA to the GO-ZnO surface. The chemical structure of the GO surface was altered by improved dispersion of GO-ZnO in organic solvents, thus enhancing the GO-ZnO dispersion in the PLLA matrix and the interface bonding with PLLA. Subsequently, composite films, GO-ZnO-PLLA and GO-ZnO-PLLA/PLLA, were prepared. The changes in interface properties and mechanical properties were studied. Furthermore, the antibacterial performance of nano-ZnO was investigated. PMID:29473891

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

Reduced Graphene Oxide-Cadmium Zinc Sulfide Nanocomposite with Controlled Band Gap for Large-Area Thin-Film Optoelectronic Device Application

NASA Astrophysics Data System (ADS)

Ibrahim, Sk; Chakraborty, Koushik; Pal, Tanusri; Ghosh, Surajit

2017-12-01

Herein, we report the one pot single step solvothermal synthesis of reduced grapheme oxide-cadmium zinc sulfide (RGO-Cd0.5Zn0.5S) composite. The reduction in graphene oxide (GO), synthesis of Cd0.5Zn0.5S (mentioned as CdZnS in the text) nanorod and decoration of CdZnS nanorods onto RGO sheet were done simultaneously. The structural, morphological and optical properties were studied thoroughly by different techniques, such as XRD, TEM, UV-Vis and PL. The PL intensity of CdZnS nanorods quenches significantly after the attachment of RGO, which confirms photoinduced charge transformation from CdZnS nanorods to RGO sheet through the interface of RGO-CdZnS. An excellent photocurrent generation in RGO-CdZnS thin-film device has been observed under simulated solar light irradiation. The photocurrent as well as photosensitivity increases linearly with the solar light intensity for all the composites. Our study establishes that the synergistic effect of RGO and CdZnS in the composite is capable of getting promising applications in the field of optoelectronic devising.

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.

The influence of the precursor compositional ratio on Cu2ZnSnS4 films prepared by using sulfurization of the metallic precursor

NASA Astrophysics Data System (ADS)

Amal, Muhamad I.; Kim, Kyoo Ho

2013-12-01

Cu2ZnSnS4 (CZTS) films were prepared by using the sulfurization of sputtered metallic precursors. The compositional ratio of the CZTS films was slightly different compared to their initial metallic precursors due to elemental loss during annealing. The Cu/(Zn+Sn) ratio for the CZTS-1, CZTS-2 and CZTS-3 films were 0.91, 1.06 and 1.21, respectively. In addition, all films had a compositional ratio of Zn/Sn >1. The grain sizes of the CZTS films increased with increasing Cu ratio. X-ray diffraction and Raman spectroscopy showed that the CZTS films with an excess of copper and zinc had secondary phases of Cu2SnS3 and ZnS. The optical band gap and absorption coefficient for all CZTS films in the range of the experimental compositions were calculated to be 1.5 eV and >104 cm-1, respectively. The presence of secondary phases related to compositional ratio in the CZTS films influenced the electrical properties. The CZTS-1 film with a Cu-poor and Zn-rich composition whose a carrier concentration, an electrical mobility, and a resistivity values were 2.29 × 1018 cm-3, 10.29 cm2 V-1 s-1, 3.16 Ω cm, is the most suitable for solar-cell applications.

Mass Measurements beyond the Major r-Process Waiting Point {sup 80}Zn

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

Baruah, S.; Herlert, A.; Schweikhard, L.

2008-12-31

High-precision mass measurements on neutron-rich zinc isotopes {sup 71m,72-81}Zn have been performed with the Penning trap mass spectrometer ISOLTRAP. For the first time, the mass of {sup 81}Zn has been experimentally determined. This makes {sup 80}Zn the first of the few major waiting points along the path of the astrophysical rapid neutron-capture process where neutron-separation energy and neutron-capture Q-value are determined experimentally. The astrophysical conditions required for this waiting point and its associated abundance signatures to occur in r-process models can now be mapped precisely. The measurements also confirm the robustness of the N=50 shell closure for Z=30.

A Co3O4-embedded porous ZnO rhombic dodecahedron prepared using zeolitic imidazolate frameworks as precursors for CO2 photoreduction

NASA Astrophysics Data System (ADS)

Wang, Tao; Shi, Li; Tang, Jing; Malgras, Victor; Asahina, Shunsuke; Liu, Guigao; Zhang, Huabin; Meng, Xianguang; Chang, Kun; He, Jianping; Terasaki, Osamu; Yamauchi, Yusuke; Ye, Jinhua

2016-03-01

Metal-organic frameworks (MOFs) are attracting considerable attention for their use as both the precursor and the template to prepare metal oxides or carbon-based materials. For the first time in this paper, the core-shell ZIF-8@ZIF-67 crystals are thermally converted into porous ZnO@Co3O4 composites by combining a seed-mediated growth process with a two-step calcination. The designed porous ZnO@Co3O4 composites exhibited the highest photocatalytic activity with an excellent stability for the reduction of CO2 among the commonly reported composite photocatalysts. Their superior photocatalytic performance is demonstrated to be resulting from the unique porous structure of ZnO@Co3O4 and the co-catalytic function of Co3O4 which can effectively suppress the photocorrosion of ZnO.Metal-organic frameworks (MOFs) are attracting considerable attention for their use as both the precursor and the template to prepare metal oxides or carbon-based materials. For the first time in this paper, the core-shell ZIF-8@ZIF-67 crystals are thermally converted into porous ZnO@Co3O4 composites by combining a seed-mediated growth process with a two-step calcination. The designed porous ZnO@Co3O4 composites exhibited the highest photocatalytic activity with an excellent stability for the reduction of CO2 among the commonly reported composite photocatalysts. Their superior photocatalytic performance is demonstrated to be resulting from the unique porous structure of ZnO@Co3O4 and the co-catalytic function of Co3O4 which can effectively suppress the photocorrosion of ZnO. Electronic supplementary information (ESI) available: Additional TG and DTA curves, XRD patterns, SEM images, TEM images, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy and GC-MS spectra of the samples. See DOI: 10.1039/c5nr08747c

Photochemical decoration of magnetic composites with silver nanostructures for determination of creatinine in urine by surface-enhanced Raman spectroscopy.

PubMed

Alula, Melisew Tadele; Yang, Jyisy

2014-12-01

In this study, silver nanostructures decorated magnetic nanoparticles for surface-enhanced Raman scattering (SERS) measurements were prepared via photoreduction utilizing the catalytic activity of ZnO nanostructure. The ZnO/Fe3O4 composite was first prepared by dispersing pre-formed magnetic nanoparticles into alkaline zinc nitrate solutions. After annealing of the precipitates, the formed ZnO/Fe3O4 composites were successfully decorated with silver nanostructures by soaking the composites into silver nitrate/ethylene glycol solution following UV irradiations. To find the optimal condition when preparing Ag@ZnO/Fe3O4 composites for SERS measurements, factors such as the reaction conditions, photoreduction time, concentration of zinc nitrate and silver nitrate were studied. Results indicated that the photoreduction efficiency was significantly improved with the assistance of ZnO but the amount of ZnO in the composite is not critical. The concentration of silver nitrate and UV irradiation time affected the morphologies of the formed composites and optimal condition in preparation of the composites for SERS measurement was found using 20mM of silver nitrate with an irradiation time of 90 min. Under the optimized condition, the obtained SERS intensities were highly reproducible with a SERS enhancement factor in the order of 7. Quantitative analyses showed that a linear range up to 1 µM with a detection limit lower than 0.1 µM in the detection of creatinine in aqueous solution could be obtained. Successful applying of these prepared composites to determine creatinine in urine sample was obtained. Copyright © 2014 Elsevier B.V. All rights reserved.

Microstructure and Mechanical Properties of Zn-Ni-Al₂O₃ Composite Coatings.

PubMed

Bai, Yang; Wang, Zhenhua; Li, Xiangbo; Huang, Guosheng; Li, Caixia; Li, Yan

2018-05-21

Zn-Ni-Al₂O₃ composite coatings with different Ni contents were fabricated by low-pressure cold spray (LPCS) technology. The effects of the Ni content on the microstructural and mechanical properties of the coatings were investigated. According to X-ray diffraction patterns, the composite coatings were primarily composed of metallic-phase Zn and Ni and ceramic-phase Al₂O₃. The energy-dispersive spectroscopy results show that the Al₂O₃ content of the composite coatings gradually decreased with increasing of Ni content. The cross-sectional morphology revealed thick, dense coatings with a wave-like stacking structure. The process of depositing Zn and Ni particles and Al₂O₃ particles by the LPCS method was examined, and the deposition mechanism was demonstrated to be mechanical interlocking. The bond strength, micro hardness and friction coefficient of the coatings did not obviously change when the Ni content varied. The presence of Al₂O₃ and Ni increased the wear resistance of the composite coatings, which was higher than that of pure Zn coatings, and the wear mechanism was abrasive and adhesive wear.

Structural, Optical, and Photocatalytic Properties of Quasi-One-Dimensional Nanocrystalline ZnO, ZnOC:nC Composites, and C-doped ZnO

NASA Astrophysics Data System (ADS)

Shalaeva, E. V.; Gyrdasova, O. I.; Krasilnikov, V. N.; Melkozerova, M. A.; Baklanova, I. V.; Buldakova, L. Yu.

Various thermolysis rotes of zinc glicolate complexes are considered for the synthesis of quasi-one-dimensional nanostructured aggregates ZnO and Zn-O-C used as photocatalysts. Structural features of quasi-one-dimensional aggregates Zn-O-C and ZnO are investigated in detail. Transmission electron microscopy, Raman spectroscopy, and electron paramagnetic resonance spectroscopy methods demonstrate that the aggregates Zn-O-C have either composite structure (ZnO crystallites in amorphous carbon matrix) or a C-doped ZnO single-phase structure depending on heat treatment conditions, and that all the aggregates exhibit as a rule a tubular morphology, a nanocrystalline structure with a high specific surface area, and a high concentration of singly charged oxygen vacancies. The mechanism of the nanocrystalline structure formation is discussed and the effect of thermolysis condition on the formation of the textured structure of aggregates is investigated. The results of examination of the photocatalytic and optical absorption properties of the synthesized aggregates are presented. The photocatalytic activity for the hydroquinone oxidation reaction under ultraviolet and visible light increases in the series: the reference ZnO powder, quasi-one-dimensional ZnO, quasi-one-dimensional aggregates C-doped ZnO, and this tendency correlates with the reduction of the optical gap width. As a result of our studies, we have arrived at an important conclusion that thermal treatment of ZnO:nC composites allows a C-doped ZnO with high catalytic activity. This increasing photoactivity of C-doped ZnO aggregates is attributed to the optimal specific surface area and electron-energy spectrum restructuring to be produced owing to the presence of singly charged oxygen vacancies and carbon dissolved in the ZnO lattice.

Effect of composition on SILAR deposited CdxZn1-xS thin films

NASA Astrophysics Data System (ADS)

Ashith V., K.; Gowrish Rao, K.

2018-04-01

In the group of II-VI compound semiconductor, cadmium zinc sulphide (CdxZn1-xS) thin films have broad application in photovoltaic, optoelectronic devices etc. For heterojunction aspects, CdxZn1-xS thin film can be used as heterojunction partner for CdTe as the absorber layer. In this work, CdZnS thin films prepared on glass substrates by Successive Ion Layer Adsorption and Reaction (SILAR) method by varying the composition. The XRD patterns of deposited films showed polycrystalline with the hexagonal phase. The crystallite size of the films was estimated from W-H plot. The bond length of the film varied w.r.to the composition of the CdxZn1-xS films. The urbach energy of the films was calcualted from absorbance data.

Optical, thermal and morphological study of ZnS doped PVA polymer nano composites

NASA Astrophysics Data System (ADS)

Guruswamy, B.; Ravindrachary, V.; Shruthi, C.; Sagar, Rohan N.; Hegde, Shreedatta

2018-05-01

The effect of ZnS nano particle doping on optical, thermal properties and morphological study of the PVA polymer has been investigated using FTIR, UV-Visible and TGA, FESEM techniques. Nano sized ZnS particles were synthesized by a simple wet chemical route. Pure and ZnS/PVA nano composites were prepared using solution casting technique. The FTIR study confirms that the ZnS nano particles interacts with the OH group of PVA polymer and forms the complex. The formation of these complexes affects the optical and thermal properties of the composite. The changes in optical properties were studied using UV-Vis absorption method. The variation in thermal property was analysed using TGA results. The modified surface morphology analysis was carried out using FESEM.

Corrosion protective performance of amino trimethylene phosphonic acid-metal complex layers fabricated on the cold-rolled steel substrate via one-step assembly

NASA Astrophysics Data System (ADS)

Yan, Ru; He, Wei; Zhai, Tianhua; Ma, Houyi

2018-06-01

Seeing that amino trimethylene phosphonic acid (ATMP) possesses very strong complexation ability to metal ions and the phosphonic acid group has good affinity for the oxidized iron surface, herein a simple and rapid film-forming method (one-step assembly method) was developed to construct the ATMP-Zn complex conversion layers (ATMP-Zn layers for short) on the cold-rolled steel (CRS) substrate. Zinc ions were found to participate in the formation process of ATMP-based composite film, which made the Zn-containing ATMP film significantly different in appearance, thickness, microstructure and film-forming mechanisms from the Zn-free ATMP film. There was mainly iron (ш) phosphonate in the Zn-free ATMP film, whereas there were Zn2+-ATMP complex and a certain amount of ZnO in the ATMP-Zn composite film. In addition, electrochemical test results clearly indicate that corrosion resistance of ATMP-Zn composite film was greatly enhanced due to the presence of Zn component. Moreover, the corrosion resistance performance could be controlled by adjusting film-forming time, pH and ATMP concentration in the film-forming solutions. The present study provides a new method for the design and fabrication of high-quality environmentally-friendly conversion layers.

Depositional conditions for the Kuna Formation, Red Dog Zn-PB-Ag-Barite District, Alaska, inferred from isotopic and chemical proxies

USGS Publications Warehouse

Johnson, Craig A.; Dumoulin, Julie A.; Burruss, Robert A.; Slack, John F.

2015-01-01

Water column redox conditions, degree of restriction of the depositional basin, and other paleoenvironmental parameters have been determined for the Mississippian Kuna Formation of northwestern Alaska from stratigraphic profiles of Mo, Fe/Al, and S isotopes in pyrite, C isotopes in organic matter, and N isotopes in bulk rock. This unit is important because it hosts the Red Dog and Anarraaq Zn-Pb-Ag ± barite deposits, which together constitute one of the largest zinc resources in the world. The isotopic and chemical proxies record a deep basin environment that became isolated from the open ocean, became increasingly reducing, and ultimately became euxinic. The basin was ventilated briefly and then became isolated again just prior to its demise as a discrete depocenter with the transition to the overlying Siksikpuk Formation. Ventilation corresponded approximately to the initiation of bedded barite deposition in the district, whereas the demise of the basin corresponded approximately to the formation of the massive sulfide deposits. The changes in basin circulation during deposition of the upper Kuna Formation may have had multiple immediate causes, but the underlying driver was probably extensional tectonic activity that also facilitated fluid flow beneath the basin floor. Although the formation of sediment-hosted sulfide deposits is generally favored by highly reducing conditions, the Zn-Pb deposits of the Red Dog district are not found in the major euxinic facies of the Kuna basin, nor did they form during the main period of euxinia. Rather, the deposits occur where strata were permeable to migrating fluids and where excess H2S was available beyond what was produced in situ by decomposition of local sedimentary organic matter. The known deposits formed mainly by replacement of calcareous strata that gained H2S from nearby highly carbonaceous beds (Anarraaq deposit) or by fracturing and vein formation in strata that produced excess H2S by reductive dissolution of preexisting barite (Red Dog deposits).

[High-precision in situ analysis of the lead isotopic composition in copper using femtosecond laser ablation MC-ICP-MS and the application in ancient coins].

PubMed

Chen, Kai-Yun; Fan, Chao; Yuan, Hong-Lin; Bao, Zhi-An; Zong, Chun-Lei; Dai, Meng-Ning; Ling, Xue; Yang, Ying

2013-05-01

In the present study we set up a femtosecond laser ablation MC-ICP-MS method for lead isotopic analysis. Pb isotopic composition of fifteen copper (brass, bronze) standard samples from the National Institute of Standards Material were analyzed using the solution method (MC-ICP-MS) and laser method (fLA-MC-ICPMS) respectively, the results showed that the Pb isotopic composition in CuPb12 (GBW02137) is very homogeneous, and can be used as external reference material for Pb isotopic in situ analysis. On CuPb12 112 fLA-MC-ICPMS Pb isotope analysis, the weighted average values of the Pb isotopic ratio are in good agreement with the results analyzed by bulk solution method within 2sigma error, the internal precision RSEs of the 208 Pb/204 Pb ratio and 207 Pb/206 Pb ratio are less than 90 and 40 ppm respectively, and the external precision RSDs of them are less than 60 and 30 ppm respectively. Pb isotope of thirteen ancient bronze coins was analyzed via fLA-MC-ICPMS, the results showed that the Pb isotopic composition of ancient coins of different dynasties is significantly different, and not all the Pb isotopic compositions in the coins even from the same dynasty are in agreement with each other.

Nondestructive atomic compositional analysis of BeMgZnO quaternary alloys using ion beam analytical techniques

NASA Astrophysics Data System (ADS)

Zolnai, Z.; Toporkov, M.; Volk, J.; Demchenko, D. O.; Okur, S.; Szabó, Z.; Özgür, Ü.; Morkoç, H.; Avrutin, V.; Kótai, E.

2015-02-01

The atomic composition with less than 1-2 atom% uncertainty was measured in ternary BeZnO and quaternary BeMgZnO alloys using a combination of nondestructive Rutherford backscattering spectrometry with 1 MeV He+ analyzing ion beam and non-Rutherford elastic backscattering experiments with 2.53 MeV energy protons. An enhancement factor of 60 in the cross-section of Be for protons has been achieved to monitor Be atomic concentrations. Usually the quantitative analysis of BeZnO and BeMgZnO systems is challenging due to difficulties with appropriate experimental tools for the detection of the light Be element with satisfactory accuracy. As it is shown, our applied ion beam technique, supported with the detailed simulation of ion stopping, backscattering, and detection processes allows of quantitative depth profiling and compositional analysis of wurtzite BeZnO/ZnO/sapphire and BeMgZnO/ZnO/sapphire layer structures with low uncertainty for both Be and Mg. In addition, the excitonic bandgaps of the layers were deduced from optical transmittance measurements. To augment the measured compositions and bandgaps of BeO and MgO co-alloyed ZnO layers, hybrid density functional bandgap calculations were performed with varying the Be and Mg contents. The theoretical vs. experimental bandgaps show linear correlation in the entire bandgap range studied from 3.26 eV to 4.62 eV. The analytical method employed should help facilitate bandgap engineering for potential applications, such as solar blind UV photodetectors and heterostructures for UV emitters and intersubband devices.

Synthesis, structural and optical properties of ZnO spindle/reduced graphene oxide composites with enhanced photocatalytic activity under visible light irradiation

NASA Astrophysics Data System (ADS)

Prabhu, S.; Pudukudy, M.; Sohila, S.; Harish, S.; Navaneethan, M.; Navaneethan, D.; Ramesh, R.; Hayakawa, Y.

2018-05-01

In the present work, spindle-shaped ZnO and reduced graphene oxide sheets were successfully synthesized by a hydrothermal method and then ZnO/r-GO composite was prepared by a direct solution mixing method. Various characterization results confirmed the interior and surface decoration of spindle-shaped ZnO on the reduced graphene oxide sheets. The phase formation, crystalline structure, morphology, surface states and optical properties were characterized using Powder X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier Transform Infrared Spectroscopy (FTIR) and UV-Vis spectroscopy. The X-ray diffraction analysis showed the formation of the hexagonal wurtzite crystalline structure of ZnO with high crystalline quality. The band gap of the ZnO/r-GO composite was found to be low (3.03eV) compared to the band gap of spindle shaped ZnO (3.13 eV), as calculated from optical studies. The spindle-like morphology of the single crystalline ZnO was clearly shown in the electron microscopic images. The chemical bonding and surface states of the samples were studied using XPS measurement. Moreover, a possible growth mechanism for the ZnO spindle was proposed. The catalytic activity of the as-synthesized samples was evaluated for the photodegradation of methylene blue under visible light irradiation. Among the synthesized samples, the ZnO/r-GO composite showed higher degradation efficiency of 93% and successfully reused for four consecutive run without any activity loss.

Solid-Phase Extraction of Hemoglobin from Human Whole Blood with a Coordination-Polymer-Derived Composite Material Based on ZnO and Mesoporous Carbon.

PubMed

Jia, Yuan; Xu, Xinxin; Ou, Jinzhao; Liu, Xiaoxia

2017-11-13

A composite material, ZnO@MC, has been synthesized successfully by calcination using a one-dimensional zinc-based coordination polymer as the precursor. In ZnO@MC, ZnO particles with a size of about 5-8 nm are dispersed evenly in a mesoporous carbon matrix. Adsorption experiments at pH 6.8 with 2 mg ZnO@MC as adsorbent illustrated an adsorption efficiency of 92.3 % in 5 mL hemoglobin (Hb) solution with a concentration of 100 mg L -1 . In contrast, the adsorption of bovine serum albumin can almost be ignored under the same conditions. The selectivity originates from a strong Zn II -histidine interaction between ZnO@MC and hemoglobin. The adsorption behavior of hemoglobin on ZnO@MC fits the Temkin model perfectly with a capacity as high as 11646 mg g -1 . The hemoglobin adsorbed on the composite material can be eluted easily with sodium dodecyl sulfate stripping reagent with an extraction efficiency of 87.7 %. Circular dichroism spectra and protein activity studies suggest the structure and biological activity of hemoglobin is the same before and after the adsorption/desorption experiment. Finally, the ZnO@MC composite material was employed to extract hemoglobin from human whole blood without any pretreatment, and gave a very satisfactory result. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Pb-Zn-Cd-Hg multi isotopic characterization of the Loire River Basin, France

NASA Astrophysics Data System (ADS)

Millot, R.; Widory, D.; Innocent, C.; Guerrot, C.; Bourrain, X.; Johnson, T. M.

2012-12-01

The contribution of human activities such as industries, agriculture and domestic inputs, becomes more and more significant in the chemical composition (major ions and pollutants such as metals) of the dissolved load of rivers. Furthermore, this influence can also be evidenced in the suspended solid matter known to play an important role in the transport of heavy metals through river systems. Human factors act as a supplementary key process. Therefore the mass-balance for the budget of catchments and river basins include anthropogenic disturbances. The Loire River in central France is approximately 1010 km long and drains an area of 117,800 km2. Initially, the Loire upstream flows in a south to north direction originating in the Massif Central, and continues up to the city of Orléans, 650 km from the source. In the upper basin, the bedrock is old plutonic rock overlain by much younger volcanic rocks. The Loire River then follows a general east to west direction to the Atlantic Ocean. The intermediate basin includes three major tributaries flowing into the Loire River from the left bank: the Cher, the Indre and the Vienne rivers; the main stream flows westward and its valley stretches toward the Atlantic Ocean. Here, the Loire River drains the sedimentary series of the Paris Basin, mainly carbonate deposits. The lower Loire basin drains pre-Mesozoic basement of the Armorican Massif and its overlying Mesozoic to Cenozoic sedimentary deposits. The Loire River is one of the main European riverine inputs to the Atlantic ocean. Here we are reporting concentration and isotope data for heavy metals Zn-Cd-Pb-Hg in river waters and suspended sediments from the Loire River Basin. In addition, we also report concentration and isotope data for these metals for the different industrial sources within the Loire Basin, as well as data for biota samples such as mussels and oysters from the Bay of Biscay and North Brittany. These organisms are known to be natural accumulators of metal pollutants. The main objective of this study is to characterize the sources and the behavior of these heavy metals in the aquatic environment, and their spatial distribution using a multi-isotope approach. Each of these isotope systematics on their own reveals important information about their geogenic or anthropogenic origin but, considered together, provide a more integrated understanding of the budgets of these pollutants within the Loire River Basin.

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.

Development of Multispectral Sandwich-Type IR Windows.

DTIC Science & Technology

1977-04-01

Coatings 52 4.4 Thermophyslcal Properties 59 4.5 Mechanical Properties 62 4.5.1 Hardness and Strength of Window Components ... 62 4.5.2 Bond...AR coating ) 51 36 Transmittance vs. wavelength for a 0.050 in. thick CVD ZnS plate (No AR coating ) 53 37 Transmittance of a ZnS/ZnSe composite...compared to 67% calculated for the ZnSe window alone. As described below, anti -reflection coatings deposited onto the composite window will further enhance

Rhelogical and antibacterial performance of sodium alginate/zinc oxide composite coating for cellulosic paper.

PubMed

Wu, Wei; Liu, Tao; He, Haibing; Wu, Xihu; Cao, Xianwu; Jin, Jia; Sun, Qijun; Roy, Vellaisamy A L; Li, Robert K Y

2018-07-01

Coating of antibacterial layer on the surface of cellulosic paper has numerous potential applications. In the present work, sodium alginate (SA) served as a binder to disperse Zn 2+ and the prepared zinc oxide (ZnO) particles were used as antibacterial agents. The rheology test revealed that there were cross-linking between Zn 2+ and SA molecular chains in the aqueous solution, resulting in the viscosity of ZnO/SA composite coating increased in the low shear rate region and decreased in the high shear rate region as compared with pure SA. SEM and EDS mapping images showed that the ZnO particles were prepared successfully at 120 °C and dispersed homogeneously on the surface of cellulose fibers and the pores of cellulosic papers. The thermal stabilities of the coated papers decreased as compared to the original blank cellulosic paper, which was ascribed to the low thermal stability of SA and the catalytic effect of ZnO on SA. The tensile stress and Young's modulus of ZnO/SA composite coated paper increased up 39.5% and 30.7%, respectively, as compared with those of blank cellulosic paper. The antibacterial activity tests indicated that the ZnO/SA composite coating endowed the cellulosic paper with effectively growth inhibition of both Gram-negative bacteria E. coli and Gram-positive bacteria S. aureu. Copyright © 2018. Published by Elsevier B.V.

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

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].

Fabrication, characterization and comparison of composite magnetic materials for high efficiency integrated voltage regulators with embedded magnetic core micro-inductors

NASA Astrophysics Data System (ADS)

Bellaredj, Mohamed L. F.; Mueller, Sebastian; Davis, Anto K.; Mano, Yasuhiko; Kohl, Paul A.; Swaminathan, Madhavan

2017-11-01

High-efficiency integrated voltage regulators (IVRs) require the integration of power inductors, which have low loss and reduced size at very high frequency. The use of a magnetic material core can reduce significantly the inductor area and simultaneously increase the inductance. This paper focuses on the fabrication, characterization and modeling of nickel zinc (NiZn) ferrite and carbonyl iron powder (CIP)-epoxy magnetic composite materials, which are used as the magnetic core materials of embedded inductors in a printed wiring board (PWB) for a system in package (SIP) based buck type IVR. The fabricated composite materials and process are fully compatible with FR4 epoxy resin prepreg and laminate. For 85% weight loading of the magnetic powder (around 100 MHz at room temperature), the composite materials show a relative permeability of 7.5-8.1 for the NiZn ferrite composite and 5.2-5.6 for the CIP composite and a loss tangent value of 0.24-0.28 for the NiZn ferrite composite and 0.09-0.1 for the CIP-composite. The room temperature saturation flux density values are 0.1351 T and 0.5280 T for the NiZn ferrite and the CIP composites, respectively. The frequency dispersion parameters of the magnetic composites are modeled using a simplified Lorentz and Landau-Lifshitz-Gilbert equation for a Debye type relaxation. Embedded magnetic core solenoid inductors were designed based on the composite materials for the output filter of a high-efficiency SIP based buck type IVR. Evaluation of a SIP based buck type IVR with the designed inductors shows that it can reach peak efficiencies of 91.7% at 11 MHz for the NiZn ferrite-composite, 91.6% at 14 MHz for CIP-composite and 87.5% (NiZn ferrite-composite) and 87.3% (CIP-composite) efficiency at 100 MHz for a 1.7 V:1.05 V conversion. For a direct 5 V:1 V conversion using a stacked topology, a peak efficiency of 82% at 10 MHz and 72% efficiency at 100 MHz can be achieved for both materials.

A Low Temperature, Solution-Processed Poly(4-vinylphenol), YO(x) Nanoparticle Composite/Polysilazane Bi-Layer Gate Insulator for ZnO Thin Film Transistor.

PubMed

Shin, Hyeonwoo; Kang, Chan-Mo; Chae, Hyunsik; Kim, Hyun-Gwan; Baek, Kyu-Ha; Choi, Hyoung Jin; Park, Man-Young; Do, Lee-Mi; Lee, Changhee

2016-03-01

Low temperature, solution-processed metal oxide thin film transistors (MEOTFTs) have been widely investigated for application in low-cost, transparent, and flexible electronics. To enlarge the application area, solution-processed gate insulators (GI) have been investigated in recent years. We investigated the effects of the organic/inorganic bi-layer GI to ZnO thin film transistors (TFTs). PVP, YO(x) nanoparticle composite, and polysilazane bi-layer showed low leakage current (-10(-8) A/cm2 in 2 MV), which are applicable in low temperature processed MEOTFTs. Polysilazane was used as an interlayer between ZnO and PVP, YO(x) nanoparticle composite as a good charge transport interface with ZnO. By applying the PVP, YO(x), nanoparticle composite/polysilazane bi-layer structure to ZnO TFTs, we successfully suppressed the off current (I(off)) to -10(-11) and fabricated good MEOTFTs in 180 degrees C.

a Facile Synthesis of Fully Porous Tazo Composite and its Remarkable Gas Sensitive Performance

NASA Astrophysics Data System (ADS)

Liang, Dongdong; Liu, Shimin; Wang, Zhinuo; Guo, Yu; Jiang, Weiwei; Liu, Chaoqian; Ding, Wanyu; Wang, Hualin; Wang, Nan; Zhang, Zhihua

The composite of a nanocrystalline SnO2 thick film deposited on an Al-doped ZnO ceramic substrate was firstly proposed. This study also provided a simple, fast and cost effective method to prepare SnO2 thick film and Al-doped ZnO ceramic as well as the final composite. The crystal structure, morphology, composition, pore size distribution and gas sensitivity of the composite were investigated by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy, Barrett-Joyner-Halenda analysis and gas sensitive measurement system. Results indicated that the composite was fully porous consisted of SnO2, ZnO and ZnAl2O4 crystal phases. The macrosized pores generated in the composite could enhance the gas infiltration into the sensing layers effectively. In this way, combining a high gas-transporting-capability and a nanocrystalline SnO2 thick film, the composite showed very impressive performance. The gas sensitivity of the composite was high enough for ethanol vapor with different concentrations, which was comparable to other kinds of reported SnO2 gas sensors, while showing two straight lines with a turning point at 1000ppm. Finally, the gas sensitive mechanism was proposed based on the microstructure and composition of the composite.

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.

Hydrothermal synthesis and characterization of hybrid Al/ZnO-GO composite for significant photodegrdation of dyes

NASA Astrophysics Data System (ADS)

Lellala, Kashinath; Namratha, K.; Sudhakar, K.; Byrappa, K.

2016-05-01

In the present work, undoped and doped Aluminum/Zinc Oxide - graphene oxide (Al/ZnO-GO) nanocomposite have been successfully synthesized by hydrothermal method from zinc acetate and aluminum nitrate solutions without using of any surfactant/stabilizing agents. The results show that the composites of GO nanosheets are decorated densely by Al/ZnO nanoparticles, which displays a good morphology and blend between GO and Al/ZnO. Hybrid composites exhibit an enhanced photocatalytic performance in reduction of dyes under UV-Vis radiation better than bare ZnO-GO and GO for methylene blue dye. The hydrothermal method leads to particles with a higher crystalline due to ambient temperature of the reaction and autogenously pressure conditions, which alters the phases and crystallizations of the nanocomposite. The optical band gap is narrowed to lower energy values due to controlled addition of aluminum and GO in the composite. The improved optical property in Al-doped ZnO flower decorated on GO can be attributed to the decrease in oxygen deficiency after Al doping. XRD, FTIR, UV-Vis spectroscopy, Raman, and Field Emission Scanning Electron Microscopy characterized the effects of Al doping on the structural characteristics and optical properties on the ZnO-GO.

Composites of ZnO nanoparticles and biomass based activated carbon: adsorption, photocatalytic and antibacterial capacities.

PubMed

Cruz, G J F; Gómez, M M; Solis, J L; Rimaycuna, J; Solis, R L; Cruz, J F; Rathnayake, B; Keiski, R L

2018-05-01

Composite material (AC-ZnO) was prepared by growing ZnO nanoparticles during the production of biomass based-activated carbon (AC) via the incorporation of zinc acetate in the process. Comprehensive analyses confirmed the presence of ZnO nanoparticles over the AC surface and described the particular nature of the composite adsorbent. Methylene blue (MB) equilibrium data fitted the Dubinin-Radushkevich model. The MB adsorption capacity was higher for the bare activated carbons (197.9-188.7 mg/g) than the activated carbons with ZnO nanoparticles (137.6-149.7 mg/g). The adsorption of the MB on the adsorbents is physical because the mean adsorption energy (E) is between 1.76 and 2.00 kJ/mol. Experiments that combine adsorption and photocatalysis were carried out with different loads of adsorbents and with and without UV-light exposure. Photocatalytic activity was identified mostly at the first stage of the adsorption process and, in the case of experiments with less load of the composite AC-ZnO, because the light obstruction effect of the activated carbon is more for higher loads. The ZnO grown over AC improves the adsorption of cations such as Pb, Al and Fe in aqueous phase (polluted river water) and provides antibacterial capacity against Escherichia coli and Salmonella typhimurium.

Hydrothermal synthesis and characterization of hybrid Al/ZnO-GO composite for significant photodegrdation of dyes

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

Lellala, Kashinath; Namratha, K.; Byrappa, K., E-mail: kashinathlellala@gmail.com, E-mail: kbyrappa@gmail.com

In the present work, undoped and doped Aluminum/Zinc Oxide - graphene oxide (Al/ZnO-GO) nanocomposite have been successfully synthesized by hydrothermal method from zinc acetate and aluminum nitrate solutions without using of any surfactant/stabilizing agents. The results show that the composites of GO nanosheets are decorated densely by Al/ZnO nanoparticles, which displays a good morphology and blend between GO and Al/ZnO. Hybrid composites exhibit an enhanced photocatalytic performance in reduction of dyes under UV-Vis radiation better than bare ZnO-GO and GO for methylene blue dye. The hydrothermal method leads to particles with a higher crystalline due to ambient temperature of themore » reaction and autogenously pressure conditions, which alters the phases and crystallizations of the nanocomposite. The optical band gap is narrowed to lower energy values due to controlled addition of aluminum and GO in the composite. The improved optical property in Al-doped ZnO flower decorated on GO can be attributed to the decrease in oxygen deficiency after Al doping. XRD, FTIR, UV-Vis spectroscopy, Raman, and Field Emission Scanning Electron Microscopy characterized the effects of Al doping on the structural characteristics and optical properties on the ZnO-GO.« less

In-situ growth of ZIF-8 on layered double hydroxide: Effect of Zn/Al molar ratios on their structural, morphological and adsorption properties.

PubMed

Yang, Yingli; Yan, Xinlong; Hu, Xiaoyan; Feng, Rui; Zhou, Min

2017-11-01

In-situ growth of Zeolite imidazolate frameworks (ZIFs) on layered double hydroxides (LDHs) to form porous composites is a promising and challenging strategy to develop materials for separation application. Herein, the Zn-Al LDH with different Zn/Al molar ratios was prepared and used as matrix for the growth of ZIF-8 on its surface. The resulting composites were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N 2 physisorption, thermogravimetric (TG), scanning electron microscope (SEM) and elemental analysis followed by testing for As V removal from aqueous solution. Results showed that ZIF-8 could form on the surface of LDH with different Zn/Al molar ratios. At low Zn/Al molar ratios, the morphology and surface area of the ZIF/LDH composites and the content of ZIF-8 in the composites were little affected by the Zn/Al molar ratio. With increasing Zn/Al molar ratio, ZIF-8/LDH exhibited a lower surface area, which resulted from reduced content of ZIF-8 caused by impurities generated in the LDH matrix. All ZIF-8/LDH samples showed high As V adsorption capacity, which was significantly higher than that of pure LDH or ZIF-8. Copyright © 2017 Elsevier Inc. All rights reserved.

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.

Geochemical constraints on the genesis of the Scheelite dome intrusion-related gold deposit, Tombstone gold belt, Yukon, Canada

USGS Publications Warehouse

Mair, J.L.; Goldfarb, R.J.; Johnson, C.A.; Hart, C.J.R.; Marsh, E.E.

2006-01-01

The Scheelite dome intrusion-related gold deposit, western Selwyn basin, Yukon, is hosted in hornfelsed metasedimentary strata that lie adjacent to the exposed apices of a monzogranite to quartz monzonite plutonic complex of the mid-Cretaceous Tombstone-Tungsten magmatic belt, Tintina gold province, Alaska and Yukon. A variety of mineralization styles occur throughout a 10- ?? 3-km east-trending corridor and include reduced Au- and W-rich skarns, Au, W- and Ag-Pb-Zn-Sb-rich quartz tension-vein arrays, and multiphase fault veins and isolated zones of Au-rich sericite-carbonate altered rock. Integrated U-Pb SHRIMP data for magmatic zircon and Ar-Ar data for magmatic and hydrotbermal biotite indicate that gold mineralization occurred within 1 to 2 m.y. of magma emplacement. Fluid inclusion, oxygen isotope, and arsenopyrite geothermometry data indicate that hydrothermal minerals formed at depths of 6 to 9 km over a temperature range from 550??C. High-temperature Au-rich skarns formed at >400??C, whereas vein-hosted mineralization formed at 280?? to 380??C. In skarns, Au is strongly associated with enrichments of Bi, Te, W, and As, whereas a variety of Au-rich veins occur, with Asrich (type 1), and Te- and W-rich (type 2) end members. Silver-Pb-Zn-Sb veins are typically Au poor and represent the latest and lowest temperature phase in the hydrothermal paragenesis. The fluid inclusion data indicate that all mineralization styles were formed from low-salinity (???4 wt % NaCl equiv) aqueous-carbonic fluids, consistent with the composition of fluid inclusions within infilled miarolitic cavities in the intrusive rocks. However, the nonaqueous fluid was predominantly CH4 in skarn, CO2 in Au-Te and Au-W veins, and a fluid with roughly equal amounts Of CO2, CH4, and N2 in Au-As and Ag-Pb-Zn-Sb veins. Oxygen isotope data are consistent with a mineralizing fluid of predominantly magmatic origin that was variably modified to more positive ??18O values during interaction with 18O-enriched metasedimentary strata. Sulfur isotope data suggest two possible sources of sulfur, a magmatic source characterized by ??34S values of approximately -5 to 0 per mil and sulfur from the metasedimentary country rocks characterized by more negative ??34S values of approximately -15 to -10 per mil. Collectively the data indicate that gold at Scheelite Dome was deposited from a magmatic-hydrothermal system. Interaction of magmatic fluids with graphitic hornfels rocks resulted in reduction of the ore fluids, higher CH4/CO2 ratios, and modification of the oxygen and sulfur isotope values of the ore fluids toward those of the metasedimentary hornfels. Progressive reduction and cooling of hydrotbermal fluids, in addition to phase separation in vein-hosted mineralization, were the mechanisms for gold deposition. Compared to other intrusion-related gold deposits associated with the Tombstone-Tungsten magmatic belt magmatism, exposed mineralization at Scheelite Dome is predominantly hosted by hornfelsed metasedimentary rocks. This results in more diverse mineralization styles and a greater spread of isotope and fluid inclusion data. ?? 2006 Society of Economic Geologists, Inc.

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.

Late-stage magmatic outgassing from a volatile-depleted Moon

PubMed Central

Moynier, Frédéric; Shearer, Charles K.

2017-01-01

The abundance of volatile elements and compounds, such as zinc, potassium, chlorine, and water, provide key evidence for how Earth and the Moon formed and evolved. Currently, evidence exists for a Moon depleted in volatile elements, as well as reservoirs within the Moon with volatile abundances like Earth’s depleted upper mantle. Volatile depletion is consistent with catastrophic formation, such as a giant impact, whereas a Moon with Earth-like volatile abundances suggests preservation of these volatiles, or addition through late accretion. We show, using the “Rusty Rock” impact melt breccia, 66095, that volatile enrichment on the lunar surface occurred through vapor condensation. Isotopically light Zn (δ66Zn = −13.7‰), heavy Cl (δ37Cl = +15‰), and high U/Pb supports the origin of condensates from a volatile-poor internal source formed during thermomagmatic evolution of the Moon, with long-term depletion in incompatible Cl and Pb, and lesser depletion of more-compatible Zn. Leaching experiments on mare basalt 14053 demonstrate that isotopically light Zn condensates also occur on some mare basalts after their crystallization, confirming a volatile-depleted lunar interior source with homogeneous δ66Zn ≈ +1.4‰. Our results show that much of the lunar interior must be significantly depleted in volatile elements and compounds and that volatile-rich rocks on the lunar surface formed through vapor condensation. Volatiles detected by remote sensing on the surface of the Moon likely have a partially condensate origin from its interior. PMID:28827322

Late-stage magmatic outgassing from a volatile-depleted Moon.

PubMed

Day, James M D; Moynier, Frédéric; Shearer, Charles K

2017-09-05

The abundance of volatile elements and compounds, such as zinc, potassium, chlorine, and water, provide key evidence for how Earth and the Moon formed and evolved. Currently, evidence exists for a Moon depleted in volatile elements, as well as reservoirs within the Moon with volatile abundances like Earth's depleted upper mantle. Volatile depletion is consistent with catastrophic formation, such as a giant impact, whereas a Moon with Earth-like volatile abundances suggests preservation of these volatiles, or addition through late accretion. We show, using the "Rusty Rock" impact melt breccia, 66095, that volatile enrichment on the lunar surface occurred through vapor condensation. Isotopically light Zn (δ 66 Zn = -13.7‰), heavy Cl (δ 37 Cl = +15‰), and high U/Pb supports the origin of condensates from a volatile-poor internal source formed during thermomagmatic evolution of the Moon, with long-term depletion in incompatible Cl and Pb, and lesser depletion of more-compatible Zn. Leaching experiments on mare basalt 14053 demonstrate that isotopically light Zn condensates also occur on some mare basalts after their crystallization, confirming a volatile-depleted lunar interior source with homogeneous δ 66 Zn ≈ +1.4‰. Our results show that much of the lunar interior must be significantly depleted in volatile elements and compounds and that volatile-rich rocks on the lunar surface formed through vapor condensation. Volatiles detected by remote sensing on the surface of the Moon likely have a partially condensate origin from its interior.

Late-stage magmatic outgassing from a volatile-depleted Moon

NASA Astrophysics Data System (ADS)

Day, James M. D.; Moynier, Frédéric; Shearer, Charles K.

2017-09-01

The abundance of volatile elements and compounds, such as zinc, potassium, chlorine, and water, provide key evidence for how Earth and the Moon formed and evolved. Currently, evidence exists for a Moon depleted in volatile elements, as well as reservoirs within the Moon with volatile abundances like Earth’s depleted upper mantle. Volatile depletion is consistent with catastrophic formation, such as a giant impact, whereas a Moon with Earth-like volatile abundances suggests preservation of these volatiles, or addition through late accretion. We show, using the “Rusty Rock” impact melt breccia, 66095, that volatile enrichment on the lunar surface occurred through vapor condensation. Isotopically light Zn (δ66Zn = -13.7‰), heavy Cl (δ37Cl = +15‰), and high U/Pb supports the origin of condensates from a volatile-poor internal source formed during thermomagmatic evolution of the Moon, with long-term depletion in incompatible Cl and Pb, and lesser depletion of more-compatible Zn. Leaching experiments on mare basalt 14053 demonstrate that isotopically light Zn condensates also occur on some mare basalts after their crystallization, confirming a volatile-depleted lunar interior source with homogeneous δ66Zn ≈ +1.4‰. Our results show that much of the lunar interior must be significantly depleted in volatile elements and compounds and that volatile-rich rocks on the lunar surface formed through vapor condensation. Volatiles detected by remote sensing on the surface of the Moon likely have a partially condensate origin from its interior.

Mass Independent Fractionation of Cadmium Isotopes During Thermal Ionization

NASA Astrophysics Data System (ADS)

Abouchami, W.; Galer, S. J.; Feldmann, H.; Schmitt, A. D.

2008-12-01

We have previously reported that Cd isotopes exhibit anomalous, non-mass dependent fractionation of odd versus even isotopes when measured by TIMS using silica gel-phosphoric acid activator. The deviation from mass dependent fractionation (MDF) on the odd masses 111 and 113 varies by fractions of a per-cent between runs. The effects cannot be explained by isobaric interferences, but seem, instead, to reflect mass independent fractionation (MIF) of Cd isotopes, much like that recently documented for Hg isotopes in natural systems (Bergquist and Blum, 2007). The absence of comparable Cd isotope anomalies in the ICP torch, and during extreme in-vacuo volatilization of Cd metal (Wombacher et al., 2004) conclusively implicates the silica gel activator in the process. So far, MIF has been documented for Cd, Zn and Pb isotopes when measured using the silica gel technique (Thirlwall, 2000; Schmitt et al., 2006; Manhes and Göpel, 2007). These MIF effects on Cd isotopes might perhaps be related to the non-mass dependence of nuclear volume with mass number, as described by Bigeleisen (1996) - also known as the "nuclear field shift". The MIF caused by the nuclear field shift results is a departure from MDF broadly characterized by a odd-even staggering with mass number. These effects have been quantified by Schauble (2007) who showed that the magnitude of the non-mass dependence for Hg and Tl isotopes lies in the ppm range for some simple reactions. Such MIF effects would appear, overall, far too small to account for our data, which require MIF offsets on the odd masses 111 and 113 approaching a per-cent. Moreover, an in-depth examination along the lines of Fujii et al. (2006) predicts tell-tale offsets for the even-even isotope pairs 114Cd/112Cd and 116Cd/112Cd as well, based upon the theory and the respective nuclear radii, but such accompanying offsets are unequivocally absent in our data. The odd-even isotope effects seen in our runs using silica gel activator are better explained by appealing to the nuclear spin (and magnetic moment) of odd nuclei alone. The "magnetic isotope effect" is a consequence of hyperfine coupling, in which an electron interacts with a nucleus of non-zero magnetic moment - i.e. one that has an odd number of nucleons (Turro, 1983; Buchachenko, 1995, 2001). This is purely a kinetic phenomenon in which the life-time, and thus the outcome, of reaction transition states is altered by the hyperfine splitting present in atoms with odd nuclei. The mechanism by which silica gel activator enhances the thermal ionization of elements such as Cd, Pb and Zn has been outlined by Kessinger and Delmore (2002). The first step involves the in-situ reduction of Cd2+ ions to Cd metal in the molten silica gel-phosphoric acid glass. It is most likely in this step - whereby two electrons are added - that a suitably long-lived transition state exists, during which the magnetic isotope effect enhances (or inhibits) reduction of masses 111 and 113 to metal species compared to those of even isotopes of Cd. The resulting "odd" and "even" populations of Cd-metal in the molten silica gel then cannot be related simply in terms of MDF. Overall, the magnetic isotope effect provides the best explanation of the MIF effects observed for Pb, Cd and Zn during thermal ionization with silica gel activator, and, probably, why the measured fractionation is always biased towards light isotopes.

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.

In-situ microwave irradiation synthesis of ZnO-graphene nanocomposite for high-performance supercapacitor applications

NASA Astrophysics Data System (ADS)

Gunaseelan, R.; Venkatachalam, V.; Raj, A. Antony

2018-04-01

In this paper, the ZnO/G nanocomposite was synthesized by facile in-situ microwave irradiation method. The as-prepared ZnO/G composite has been characterized with X-ray powder diffraction. The electrochemical properties of the obtained composite electrode for supercapacitor have been studied by cyclic voltammetry and electrochemical impedance spectra analyses. The ZnO/G nanocomposites showed a good capacitive behavior with a higher specific capacitance of 140.4 F/g at a scan rate of 5 mV/s scan rate in 1M KOH electrolyte. Based on the electrochemical results revealed that the composite electrode is a suitable candidate for supercapacitor applications.

[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.

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.

ZnO-based ultra-violet light emitting diodes and nanostructures fabricated by atomic layer deposition

NASA Astrophysics Data System (ADS)

Chen, Miin-Jang; Yang, Jer-Ren; Shiojiri, Makoto

2012-07-01

We have investigated ZnO-based light-emitting diodes (LEDs) fabricated by atomic layer deposition (ALD), demonstrating that ALD is one of the noteworthy techniques to prepare high-quality ZnO required for ultraviolet (UV) photonic devices. Here, we review our recent investigations on different ZnO-based heterojunction LEDs such as n-ZnO/p-GaN LEDS, n-ZnO:Al/ZnO nanodots-SiO2 composite/p-GaN LEDS, n-ZnO/ZnO nanodots-SiO2 composite/p-AlGaN LEDs, n-ZnO:Al/i-ZnO/p-SiC(4H) LEDs, and also on ZnO-based nanostructures including ZnO quantum dots embedded in SiO2 nanoparticle layer, ZnO nanopillars on sapphire substrates, Al-doped ZnO films on sapphire substrate and highly (0 0 0 1)-oriented ZnO films on amorphous glass substrate. The latest investigation also demonstrated p-type ZnO:P films prepared on amorphous silica substrates, which allow us to fabricate ZnO-based homojunction LEDs. These devices and structures were studied by x-ray diffraction and various analytical electron microscopy observations as well as electric and electro-optical measurements.

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.

Enhanced photobactericidal activity of ZnO nanorods modified by meso-tetrakis(4-sulfonatophenyl)porphyrin under visible LED lamp irradiation.

PubMed

Rahimi, Rahmatollah; Shokraiyan, Javad; Rabbani, Mahboubeh; Fayyaz, Fatemeh

2015-01-01

In this study, zinc oxide (ZnO) nanorods have been synthesized using a simple template-free precipitation technique and deposited on glass substrate. The meso-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) has been synthesized and then immobilized on the surface of ZnO nanorods to prepare an organic/inorganic composite. The samples were characterized by various techniques such as X-ray diffraction, diffuse reflectance spectra, Fourier transform-infrared spectroscopy and scanning electron microscopy. In addition, the photobactericidal activity of TPPS/ZnO composite, TPPS and ZnO nanorods was tested against the pathogenic bacterium of Escherichia coli under visible LED lamp irradiation. The results indicate that the photobactericidal activity of TPPS-loaded ZnO nanorods was better than TPPS or ZnO nanorods, separately.

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.

Characterization of 68Zn uptake, translocation, and accumulation into developing grains and young leaves of high Zn-density rice genotype*

PubMed Central

Wu, Chun-yong; Feng, Ying; Shohag, Md. Jahidul Islam; Lu, Ling-li; Wei, Yan-yan; Gao, Chong; Yang, Xiao-e

2011-01-01

Zinc (Zn) is an essential micronutrient for humans, but Zn deficiency has become serious as equally as iron (Fe) and vitamin A deficiencies nowadays. Selection and breeding of high Zn-density crops is a suitable, cost-effective, and sustainable way to improve human health. However, the mechanism of high Zn density in rice grain is not fully understood, especially how Zn transports from soil to grains. Hydroponics experiments were carried out to compare Zn uptake and distribution in two different Zn-density rice genotypes using stable isotope technique. At seedling stage, IR68144 showed higher 68Zn uptake and transport rate to the shoot for the short-term, but no significant difference was observed in both genotypes for the long-term. Zn in xylem sap of IR68144 was consistently higher, and IR68144 exhibited higher Zn absorption ratio than IR64 at sufficient (2.0 µmol/L) or surplus (8.0 µmol/L) Zn supply level. IR64 and IR68144 showed similar patterns of 68Zn accumulation in new leaves at seedling stage and in developing grains at ripening stage, whereas 68Zn in new leaves and grains of IR68144 was consistently higher. These results suggested that a rapid root-to-shoot translocation and enhanced xylem loading capacity may be the crucial processes for high Zn density in rice grains. PMID:21528496

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

Co-precipitation synthesis of nano-composites consists of zinc and tin oxides coatings on glass with enhanced photocatalytic activity on degradation of Reactive Blue 160 KE2B.

PubMed

Habibi, Mohammad Hossein; Mardani, Maryam

2015-02-25

Nano-composite containing zinc oxide-tin oxide was obtained by a facile co-precipitation route using tin chloride tetrahydrate and zinc chloride as precursors and coated on glass by Doctor Blade deposition. The crystalline structure and morphology of composites were evaluated by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). The XRD results showed peaks relative to zinc oxide with hexagonal wurtzite structure and tin oxide with tetragonal structure. FESEM observations showed that the nano-composite consisted of aggregates of particles with an average particle size of 18 nm. The photocatalytic activity of the pure SnO2, pure ZnO, ZnSnO3-Zn2SnO4 and ZnO-SnO2 nano-structure thin films was examined using the degradation of a textile dye Reactive Blue 160 (KE2B). ZnO-SnO2 nano-composite showed enhanced photo-catalytic activity than the pure zinc oxide and tin oxide. The enhanced photo-catalytic activity of the nano-composite was ascribed to an improved charge separation of the photo-generated electron-hole pairs. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Synthesis and characterization of Mn-ZnFe2O4 and Mn-ZnFe2O4/rGO nanocomposites from waste batteries for photocatalytic, electrochemical and thermal studies

NASA Astrophysics Data System (ADS)

Mylarappa, M.; Venkata Lakshmi, V.; Vishnu Mahesh, K. R.; Nagaswarupa, H. P.; Raghavendra, N.

2017-11-01

In the present paper, Mn-ZnFe2O4 and Mn-ZnFe2O4/rGO composites recovered from waste batteries using acid dissolution and ferrite processing were studied. The recovered Mn-ZnFe2O4 nanocomposites were decorated onto rGO using the facile hydrothermal method. The recovered material was characterized using x-ray powder diffraction to study the particle size and crystallinity. The morphology of the composites was analyzed using scanning electron microscopy, and elements present in the materials were studied using energy dispersive x-ray analysis. The functional groups attached were observed using a Fourier transform infrared spectrometer. Furthermore, the recovered composites were evaluated in thermal studies using thermal gravimetric analysis, differential scanning calorimetry and dynamic thermal analysis. The material was used as a photocatalyst for the removal of acid orange 88 dye, and as an electrocatalyst. The decreased band gap energy for the Mn-ZnFe2O4/rGO composite was displayed in better photocatalytic activity for a given reaction. The electrochemical properties of Mn-ZnFe2O4 and Mn-ZnFe2O4/rGO have been investigated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) with a paste-type electrode. The CV indicated the reversibility of the electrode reaction, and the EIS revealed that a decrease in the charge transfer resistance increases the double layer capacitance of the rGO/Mn-ZnFe2O4 electrode.

Spectroscopic analyses on sonocatalytic damage to bovine serum albumin (BSA) induced by ZnO/hydroxylapatite (ZnO/HA) composite under ultrasonic irradiation

NASA Astrophysics Data System (ADS)

Wang, Zhiqiu; Li, Ying; Wang, Jun; Zou, Mingming; Gao, Jingqun; Kong, Yumei; Li, Kai; Han, Guangxi

ZnO/hydroxylapatite (ZnO/HA) composite with HA molar content of 6.0% was prepared by the method of precipitation and heat-treated at 500 °C for 40 min and was characterized by powder X-ray diffraction (XRD). The sonocatalytic activities of ZnO/HA composite was carried out through the damage of bovine serum albumin (BSA) in aqueous solution. Furthermore, the effects of several factors on the damage of BSA molecules were evaluated by means of UV-vis and fluorescence spectra. Experimental results indicated that the damage degree of BSA aggravated with the increase of ultrasonic irradiation time, irradiation power and ZnO/HA addition amount, but weakened with the increase of solution acidity and ionic strength. In addition, the damage site to BSA was also studied by synchronous fluorescence technology and the damage site was mainly at tryptophan (Trp) residue. This paper provides a valuable reference for driving sonocatalytic method to treat tumor in clinic application.

Kinetics and equilibrium models for the sorption of tributyltin to nZnO, activated carbon and nZnO/activated carbon composite in artificial seawater.

PubMed

Ayanda, Olushola S; Fatoki, Olalekan S; Adekola, Folahan A; Ximba, Bhekumusa J

2013-07-15

The removal of tributyltin (TBT) from artificial seawater using nZnO, activated carbon and nZnO/activated carbon composite was systematically studied. The equilibrium and kinetics of adsorption were investigated in a batch adsorption system. Equilibrium adsorption data were analyzed using Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R) isotherm models. Pseudo first- and second-order, Elovich, fractional power and intraparticle diffusion models were applied to test the kinetic data. Thermodynamic parameters such as ΔG°, ΔS° and ΔH° were also calculated to understand the mechanisms of adsorption. Optimal conditions for the adsorption of TBT from artificial seawater were then applied to TBT removal from natural seawater. A higher removal efficiency of TBT (>99%) was obtained for the nZnO/activated carbon composite material and for activated carbon but not for nZnO. Copyright © 2013 Elsevier Ltd. All rights reserved.

Fabrication of hierarchical porous ZnO/NiO hollow microspheres for adsorptive removal of Congo red

NASA Astrophysics Data System (ADS)

Lei, Chunsheng; Pi, Meng; Cheng, Bei; Jiang, Chuanjia; Qin, Jiaqian

2018-03-01

Hierarchical porous zinc oxide (ZnO)/nickel(II) oxide (NiO) hollow microspheres were fabricated by a facile hydrothermal approach and subsequent calcination process. The synthesized samples were used as adsorbent for removing Congo red (CR), a commercial azo dye. The synthesized hierarchical porous ZnO/NiO composites exhibit a superior adsorption capacity for CR (518 mg/g), compared with pure NiO (397 mg/g) and ZnO (304 mg/g). The high CR adsorption capacity of ZnO/NiO composites was associated with its hierarchical porous hollow structures and large specific surface area (130 m2/g), which provide a large quantity of active sites for CR molecules. The adsorption kinetics data were perfectly fitted to a pseudo-second-order model. The isotherms were accurately described by the Langmuir model. The results suggest that the as-prepared hierarchical porous ZnO/NiO composites are a highly efficient adsorbent for treating organic dye-impacted wastewater.

Electronic and chemical structure of an organic light emitter embedded in an inorganic wide-bandgap semiconductor: Photoelectron spectroscopy of layered and composite structures of Ir(BPA) and ZnSe

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

Dimamay, Mariel; Laboratoire de Chimie des Polymères Organiques, CNRS, Université de Bordeaux, UMR 5629-16 Avenue Pey-Berland, 33607 Pessac; Mayer, Thomas

Luminescent organic phases embedded in conductive inorganic matrices are proposed for hybrid organic-inorganic light-emitting diodes. In this configuration, the organic dye acts as the radiative recombination site for charge carriers injected into the inorganic matrix. Our investigation is aimed at finding a material combination where the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the organic dye are situated in between the valence and conduction bands of the inorganic matrix in order to promote electron and hole transfer from the matrix to the dye. Bilayer and composite thin films of zinc selenide (ZnSe) and a redmore » iridium complex (Ir(BPA)) organic light emitter were prepared in situ via UHV thermal evaporation technique. The electronic and atomic structures were studied applying X-ray and ultraviolet photoelectron spectroscopies. The measured energy band alignments for the ZnSe/Ir(BPA) bilayer and ZnSe+Ir(BPA) composite reveal that the HOMO and LUMO of the organic dye are positioned in the ZnSe bandgap. For the initial steps of ZnSe deposition on a dye film to form Ir(BPA)/ZnSe bilayers, zinc atoms intercalate into the dye film leaving behind an excess of selenium at the interface that partly reacts with dye molecules. Photoelectron spectroscopy of the composites shows the same species suggesting a similar mechanism. This mechanism leads to composite films with increased content of amorphous phases in the inorganic matrix, thereby affecting its conductivity, as well as to the presence of nonradiative recombination sites provided by the intercalated Zn atoms.« less

Zn2+ in-situ substitution behavior during the formation of BaTiO3 coatings from plasma-sprayed powders collected in liquid nitrogen

NASA Astrophysics Data System (ADS)

Liu, Zhe; Xing, Zhiguo; Wang, Haidou; Xue, Zifan; Chen, Shuying; Cui, Xiufang; Jin, Guo

2018-04-01

The dielectric performance of BaTiO3 ceramic coatings is enhanced significantly by the addition of ZnO. In this study, the maximum relative permittivity value (εr ≈ 923) was measured in BaTiO3 coatings with ZnO added at 6 wt%. The Curie temperature (Tc) was in the range of 111 °C-121 °C for all of the ZnO-modified BaTiO3 coatings. Tc shifted to low temperatures as the ZnO content increased. Detailed analyses were performed to determine the phase composition and optical band gaps of powders collected in liquid nitrogen, which showed that the Zn2+ ions were incorporated into the BaTiO3 lattice where they substituted into the Ti4+ sites, and the composite powders (BaTiO3 + 6 wt% ZnO) tolerated high temperatures in the plasma beam. In addition, some residual Zn accumulated in the grain boundary in the form of ZnO. X-ray diffraction and Raman spectroscopy showed that the substitution led to changes in the compositional and structural properties. The red shift in the optical band gap of BaTiO3 indicated that the ZnTi'' defects caused by the dopants acted as carriers in the doped BaTiO3 coatings.

ZnO/graphite composites and its antibacterial activity at different conditions.

PubMed

Dědková, Kateřina; Janíková, Barbora; Matějová, Kateřina; Čabanová, Kristina; Váňa, Rostislav; Kalup, Aleš; Hundáková, Marianna; Kukutschová, Jana

2015-10-01

The paper reports laboratory preparation, characterization and in vitro evaluation of antibacterial activity of ZnO/graphite nanocomposites. Zinc chloride and sodium carbonate served as precursors for synthesis of zinc oxide, while micromilled and natural graphite were used as the matrix for ZnO nanoparticles anchoring. During the reaction of ZnCl2 with saturated aqueous solution of Na2CO3a new compound is created. During the calcination at the temperature of 500 °C this new precursors decomposes and ZnO nanoparticles are formed. Composites ZnO/graphite with 50 wt.% of ZnO particles were prepared. X-ray powder diffraction and Raman microspectroscopy served as phase-analytical methods. Scanning electron microscopy technique was used for morphology characterization of the prepared samples and EDS mapping for visualization of elemental distribution. A developed modification of the standard microdilution test was used for in vitro evaluation of daylight induced antibacterial activity and antibacterial activity at dark conditions. Common human pathogens served as microorganism for antibacterial assay. Antibacterial activity of ZnO/graphite composites could be based on photocatalytic reaction; however there is a role of Zn(2+) ions on the resulting antibacterial activity which proved the experiments in dark condition. There is synergistic effect between Zn(2+) caused and reactive oxygen species caused antibacterial activity. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

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.

Microstructure and Mechanical Properties of Zn-Ni-Al2O3 Composite Coatings

PubMed Central

Bai, Yang; Wang, Zhenhua; Li, Xiangbo; Huang, Guosheng; Li, Caixia

2018-01-01

Zn-Ni-Al2O3 composite coatings with different Ni contents were fabricated by low-pressure cold spray (LPCS) technology. The effects of the Ni content on the microstructural and mechanical properties of the coatings were investigated. According to X-ray diffraction patterns, the composite coatings were primarily composed of metallic-phase Zn and Ni and ceramic-phase Al2O3. The energy-dispersive spectroscopy results show that the Al2O3 content of the composite coatings gradually decreased with increasing of Ni content. The cross-sectional morphology revealed thick, dense coatings with a wave-like stacking structure. The process of depositing Zn and Ni particles and Al2O3 particles by the LPCS method was examined, and the deposition mechanism was demonstrated to be mechanical interlocking. The bond strength, micro hardness and friction coefficient of the coatings did not obviously change when the Ni content varied. The presence of Al2O3 and Ni increased the wear resistance of the composite coatings, which was higher than that of pure Zn coatings, and the wear mechanism was abrasive and adhesive wear. PMID:29883391

Power generation from base excitation of a Kevlar composite beam with ZnO nanowires

NASA Astrophysics Data System (ADS)

Malakooti, Mohammad H.; Hwang, Hyun-Sik; Sodano, Henry A.

2015-04-01

One-dimensional nanostructures such as nanowires, nanorods, and nanotubes with piezoelectric properties have gained interest in the fabrication of small scale power harvesting systems. However, the practical applications of the nanoscale materials in structures with true mechanical strengths have not yet been demonstrated. In this paper, piezoelectric ZnO nanowires are integrated into the fiber reinforced polymer composites serving as an active phase to convert the induced strain energy from ambient vibration into electrical energy. Arrays of ZnO nanowires are grown vertically aligned on aramid fibers through a low-cost hydrothermal process. The modified fabrics with ZnO nanowires whiskers are then placed between two carbon fabrics as the top and the bottom electrodes. Finally, vacuum resin transfer molding technique is utilized to fabricate these multiscale composites. The fabricated composites are subjected to a base excitation using a shaker to generate charge due to the direct piezoelectric effect of ZnO nanowires. Measuring the generated potential difference between the two electrodes showed the energy harvesting application of these multiscale composites in addition to their superior mechanical properties. These results propose a new generation of power harvesting systems with enhanced mechanical properties.

Characterization of thermal destruction behavior of hybrid composites based on polyoxymethylene, ethylene-octene copolymer impact modifier and ZnO nanofiller

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

Meri, Remo Merijs; Zicans, Janis; Abele, Agnese

Hybrid polymer nanocomposites, composed of polyoxymethylene (POM), ethylene octene copolymer (EOC) and plasma synthesized tetrapod shaped zinc oxide (ZnO), were prepared by using melt compounding. The content of EOC in the POM based composites was varied between 10 and 50 mass %, while the content of ZnO was constant (2 mass %). Thermal behaviour of POM based systems was studied by using thermogravimetric analysis coupled with Fourier transform infrared spectroscopy. The influence of the elastomer content and/or ZnO addition on the thermal stability of POM based systems was evaluated. The influence of the α-octene content in the elastomer on themore » thermal decomposition behaviour of POM and its nanocomposites with ZnO was also evaluated. Results of thermogravimetric analysis showed that, by rising either the elastomer or ZnO content, thermal stability of the investigated POM composites was increased. The modifying effect of EOC17 in respect of thermal resistance was somewhat larger than that of EOC38 because of the smaller amount of tertiary carbon atoms in the macromolecular structure of the former elastomer. Improved thermal resistance of ZnO containing POM based composites was because of impermeable structure the inorganic nanofiller allowing decrease gas exchange rate and facilitating non-combustible gases, such as CO{sub 2}, stay in the zone of burning. Addition of ZnO have a potential to influence structure of the polymer blend matrix itself by improving its barrier characteristics.« less

COPPER-64 Production Studies with Natural Zinc Targets at Deuteron Energy up to 19 Mev and Proton Energy from 141 Down to 31 Mev

NASA Astrophysics Data System (ADS)

Bonardi, Mauro L.; Birattari, Claudio; Groppi, Flavia; Song Mainard, Hae; Zhuikov, Boris L.; Kokhanyuk, Vladimir M.; Lapshina, Elena V.; Mebel, Michail V.; Menapace, Enzo

2004-07-01

High specific activity no-carrier-added 64Cu is a β-/β+ emitting radionuclide of increasing interest for PET imaging, as well as systemic and targeted radioimmunotherapy of tumors. Its peculiarity of intense Auger emitter is still under investigation. The cross-sections for production of 64Cu from Zn target of natural isotopic composition were measured in the deuteron energy range from threshold up to 19 MeV and proton energy range from 141 down to 31 MeV. The stacked-foil technique was used at both K=38 cyclotron of JRC-Ispra of CEC, Italy and 160 MeV intersection point of INR proton-LINAC in Troitsk, Russia. Several Ga, Zn, Cu, Ni, Co, V, Fe and Mn radionuclides were detected in Zn targets at the EOB. Optimized irradiation conditions are reported as a function of deuteron energy and energy loss into the Zn target, as well as target irradiation time and cooling time after radiochemistry. The activity of n.c.a. 64Cu was measured through its only γ emission of 1346 keV (i.e. 0.473 % intensity) both by instrumental and radiochemical methods, due to the non-specificity of annihilation radiation at 511 keV. To this last purpose, it was necessary to carry out a selective radiochemical separation of GaIII radionuclides by liquid/liquid extraction from the bulk of irradiated Zn targets and other spallation products, which remained in the 7 M HCl aqueous phase. Anion exchange chromatography tests had been carried out to separate the 64Cu from all others radionuclides in n.c.a. form. Theoretical calculations of cross-sections were performed with codes EMPIRE II and PENELOPE for deuteron reactions and CEF model and HMS-ALICE hybrid model for proton reactions. The theoretical results are presented and compared with the experimental values.