478 results on '"Isotopes of copper"'
Search Results
2. Nucleon Densities of Copper Isotopes Calculated by Skyrme and Gogny Models
- Author
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İsmail Hakkı Sarpün, Eyyup Tel, Abdullah Aydin, and Ferhan Akdeniz
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Physics ,Science (General) ,skyrme ,Isotopes of copper ,Nuclear Theory ,General Medicine ,hartree-fock ,gogny ,nucleon density ,Nuclear physics ,Q1-390 ,Physics::Atomic Physics ,Nuclear Experiment ,Nucleon - Abstract
The ground state properties of the nuclei are generally calculated using two different methods, namely Skyrme and Gogny force methods. We have calculated nucleon densities of Copper isotopes by using Hartree-Fock-Skyrme (using Woods-Saxon Potential) (SHF-WS), Hartree-Fock-Skyrme (using Harmonic Oscillator Potential) (SHF-HO), Hartree-Fock-Bogolyubov-Skyrme (HFB-S) and the Hartree-Fock-Bogolyubov-Gogny (HFB-G) methods. In the first two methods, the densities and rms (root mean square) radii for both proton and neutron of copper isotopes were calculated by different Skyrme parameters set. Theoretical calculated charge density was compared with experimental data of Angeli and Marinova to determine the best parameter set for each copper isotope. Then all evaluated nucleon densities via four different methods were compared each other. All methods gave similar results for all copper isotopes.
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- 2021
3. Fractionation of the copper, oxygen and hydrogen isotopes between malachite and aqueous phase
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Ryan Mathur, Alexandra M. Plumhoff, Juraj Majzlan, and Rastislav Milovský
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010504 meteorology & atmospheric sciences ,Hydrogen ,Chemistry ,Stable isotope ratio ,Isotopes of copper ,Inorganic chemistry ,chemistry.chemical_element ,Malachite ,Fractionation ,010502 geochemistry & geophysics ,01 natural sciences ,Oxygen ,Redox ,Copper ,Geochemistry and Petrology ,visual_art ,visual_art.visual_art_medium ,0105 earth and related environmental sciences - Abstract
Studies of the equilibrium isotope properties of stable isotopes of minerals have been initiated principally because of their application to the solution of geochemical problems. Therefore, we examined malachite, a common secondary mineral in the oxidation zone of ore deposits. Stable isotope characterization can contribute needed information on the formation of malachite by establishing the isotopic composition of the parental waters. The equilibrium oxygen and hydrogen isotope fractionations between malachite and solution were determined by precipitation experiments over the temperature range from 10 to 65 °C and could be distinguished in two sets of fractionation factors depending on the temperature. For 45–65 °C, the fractionation is expressed as 1000 ln α mal - sol oxygen = 2.87 ( 10 6 / T 2 ) + 0.96 and 1000 ln α mal - sol hydrogen = - 1.47 ( 10 6 / T 2 ) - 22.3 with temperature (T) in Kelvin. With the application of the fractionation factors of oxygen and hydrogen of malachite onto source water from the meteoric water line, we were able to calculate the “malachite line” which represents the isotopic compositions of malachite that would precipitate from such water. We also examined the copper isotope fractionation factors between solution and malachite from 10 to 65 °C: 1000 ln α sol - mal copper = 0.033 ( 10 6 / T 2 ) - 0.19 with fractionation shift of Δ 65 Cu malachite - solution = - 0.17 ± 0.05 ‰. This fractionation shift implies that chemical reactions without change of the redox state yield only minor copper isotope fractionation. The calculated fractionation factors of oxygen and hydrogen were used to determine the oxygen and hydrogen isotopic composition of the parental waters of natural malachite samples from a number of localities worldwide. With δ 18 O VSMOW values of +22.1 to +29.5 ‰ and δ D values of - 132 to - 61 ‰ for the natural malachite and δ 18 O VSMOW values of - 14.5 to - 7 ‰ and δ D values of - 107 to - 36 ‰ for the parental water together with the Cu isotopes, it is to assume that all investigated malachite samples are supergene samples which formed from meteoric water. Even in massive malachite samples from Ural Mts. (Russia), no signs of other fluids were detected from the isotopic composition.
- Published
- 2021
4. Chalcopyrite-dissolved Cu isotope exchange at hydrothermal conditions: Experimental constraints at 350 °C and 50 MPa
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William E. Seyfried, David M. Borrok, Spencer Niebuhr, and Drew D. Syverson
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Recrystallization (geology) ,010504 meteorology & atmospheric sciences ,Isotope ,Chalcopyrite ,Isotopes of copper ,Chemistry ,Analytical chemistry ,Fractionation ,010502 geochemistry & geophysics ,01 natural sciences ,Equilibrium fractionation ,Hydrothermal circulation ,Geochemistry and Petrology ,Mass transfer ,visual_art ,visual_art.visual_art_medium ,0105 earth and related environmental sciences - Abstract
This study presents experimental copper isotope (65Cu/63Cu) fractionation data between chalcopyrite and dissolved Cu at physiochemical conditions representative of high temperature mid-ocean ridge hydrothermal environments. The experimental data are compared with chemical and Cu isotope data from high temperature fluids and chalcopyrite sampled from the Main Endeavour Field and ASHES hydrothermal fields located along the Juan de Fuca Ridge. Specifically, three long-term (>250–2500 hr) chalcopyrite recrystallization experiments were conducted at 350 °C and 50 MPa in acidic chloride-bearing fluid. One of the experiments contained 57Fe isotope tracer to quantify reaction progress and the extent of exchange between chalcopyrite and dissolved Fe, which serves as a proxy for Cu isotope exchange ( Syverson et al., 2017 ). The dissolved 57Fe tracer demonstrated rapid isotope exchange between chalcopyrite and dissolved metals within the duration of the long term experiments, approximately 2500 hr, where complete exchange was achieved within approximately 1000 hr. The experimentally determined δ65Cu equilibrium fractionation between chalcopyrite and dissolved Cu, Δ 65 C u [ C p y - C u a q ] = −0.22 ± 0.16‰ (1σ), is comparable in sign and magnitude to theoretical predictions. Comparison of the δ65Cu values of chimney-derived chalcopyrite and hydrothermal fluids sampled from the Main Endeavour Field and ASHES hydrothermal systems demonstrate a range in (dis)equilibrium from theoretical and experimental Δ 65 C u [ C p y - C u a q ] constraints, possibly due to temporal fluctuations in the δ65Cu value of hydrothermal fluid associated with changes in the physiochemical processes controlling Cu mass transfer in the subseafloor. Overall, the small Δ 65 C u [ C p y - C u a q ] effectively allows chalcopyrite to be a reliable recorder of the variability in the δ65Cu value of end-member hydrothermal fluids throughout the temporal evolution of MOR hydrothermal systems.
- Published
- 2021
5. A Potential New Chalcopyrite Reference Material for LA‐MC‐ICP‐MS Copper Isotope Ratio Measurement
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Chunlei Zong, Honglin Yuan, Kaiyun Chen, Yan Luan, Nan Lv, Xiaohui Sun, and Zhian Bao
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Geochemistry and Petrology ,Chemistry ,Mc icp ms ,Isotopes of copper ,Chalcopyrite ,visual_art ,visual_art.visual_art_medium ,Analytical chemistry ,Geology ,Ratio measurement - Published
- 2021
6. Self-Consistent Calculation of the Charge Radii in a Long $${}^{\mathbf{58{-}82}}$$Cu Isotopic Chain
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Ivan Borzov and S. V. Tolokonnikov
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Physics ,Nuclear and High Energy Physics ,Basis (linear algebra) ,010308 nuclear & particles physics ,Isotopes of copper ,Nuclear Theory ,Shell (structure) ,Charge (physics) ,01 natural sciences ,Atomic and Molecular Physics, and Optics ,Chain (algebraic topology) ,0103 physical sciences ,Neutron ,Nabla symbol ,Atomic physics ,Nuclear Experiment ,010306 general physics ,Fermi Gamma-ray Space Telescope - Abstract
The charge radii are calculated in long chain of copper isotopes that includes the $${}^{58,79}$$ Cu exotic nuclei, which are close to the doubly magic nuclei of $${}^{58,78}$$ Ni, and the nuclei featuring the $$N=32$$ , $$34$$ , and $$40$$ magic subshells. Use is made of the self-consistent theory of finite Fermi systems and the family of energy density functionals proposed by Fayans and his coauthors (DF3, DF3-a, …). The results are compared with experimental data and with the results of the calculations based on self-consistent models that employ new versions of the Fayans functional—Fy(std) and Fy(HFB, $$\nabla r$$ ), whose parameters were obtained by means of an extended optimization protocol—as well as with the results of ab-initio calculations performed on the basis of the renormalization-group model and with the results of the calculation with a density-dependent spin–orbit interaction stemming from three-nucleon forces. The weakening of odd–even staggering of radii of nuclei in the ISOLDE-CERN experiments as the nuclei approach the $$N=50$$ closed neutron shell is analyzed, and the possible mechanisms behind this weakening are considered. It is shown that the isotopic dependences of the charge radii and the total beta-decay energies are correlated.
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- 2020
7. Evaluating copper isotope fractionation in the metallurgical operational chain: An experimental approach
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T. Rose and Sabine Klein
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Archeology ,History ,Chemistry ,Isotopes of copper ,visual_art ,Metallurgy ,visual_art.visual_art_medium ,Slag ,Fractionation ,Mass spectrometry - Published
- 2020
8. Copper Isotopes in Theranostics
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Gianluca Valentini and Bianca Gutfilen
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Chemistry ,Isotopes of copper ,Radiochemistry - Published
- 2022
9. Copper Isotope Variations During Magmatic Migration in the Mantle: Insights From Mantle Pyroxenites in Balmuccia Peridotite Massif
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Marina Lazarov, Zaicong Wang, Harry Becker, Xianlei Geng, Zhaochu Hu, Zongqi Zou, and Ming Li
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Peridotite ,geography ,Geophysics ,geography.geographical_feature_category ,Space and Planetary Science ,Geochemistry and Petrology ,Isotopes of copper ,Earth and Planetary Sciences (miscellaneous) ,Geochemistry ,Igneous differentiation ,Massif ,Mantle (geology) ,Geology - Published
- 2019
10. Copper Isotopes and Copper to Zinc Ratio as Possible Biomarkers for Thyroid Cancer
- Author
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Lutz Schomburg, Yahia Harek, P. Telouk, Nouria Dennouni-Medjati, Julian Hackler, Alexandra T. Gourlan, Qian Sun, Moussa Belhadj, Laurent Charlet, Majda Dali-Sahi, and Latifa Sarra Kazi Tani
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Medicine (General) ,medicine.medical_specialty ,Isotopes of copper ,chemistry.chemical_element ,Zinc ,Thyroid carcinoma ,R5-920 ,Internal medicine ,thyroid cancer ,medicine ,Thyroid cancer ,isotopes ,Original Research ,zinc ,Thyroid ,biomarkers ,Cancer ,General Medicine ,Micronutrient ,medicine.disease ,Endocrinology ,medicine.anatomical_structure ,chemistry ,copper ,Medicine ,Biomarker (medicine) - Abstract
Thyroid cancer is the most common endocrine cancer. There is no systematic screening for such cancer, and the current challenge is to find potential biomarkers to facilitate an early diagnosis. Copper (Cu) and zinc (Zn) are essential micronutrients involved in the proper functioning of the thyroid gland, and changes in their concentrations have been observed in the development of cancer. Previous studies have highlighted the potential 65Cu/63Cu ratio (δ65Cu) to be a cancer biomarker. This study tests its sensitivity on plasma samples (n = 46) of Algerian patients with papillary thyroid carcinoma and a set of corresponding biopsies (n = 11). The δ65Cu ratio in blood and tumor samples was determined using multi collector inductively coupled plasma-mass spectrometry (MC-ICP-MS), and their corresponding Cu and Zn plasma total concentrations using total reflection X-ray fluorescence (TXRF). Plasma concentrations of Cu were significantly higher (1346.1 ± 328.3 vs. 1060.5 ± 216.1 μg/L, p < 0.0001), and Zn significantly lower (942.1 ± 205.2 vs. 1027.9 ± 151.4 μg/L, p < 0.05) in thyroid cancer patients as compared to healthy controls (n = 50). Accordingly, the Cu/Zn ratio was significantly different between patients and controls (1.5 ± 0.4 vs. 1.0 ± 0.3, p < 0.0001). Furthermore, the δ65Cu plasma levels of patients were significantly lower than healthy controls (p < 0.0001), whereas thyroid tumor tissues presented high δ65Cu values. These results support the hypothesis that Cu isotopes and plasma trace elements may serve as suitable biomarkers of thyroid cancer diagnosis.
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- 2021
11. Revealing ancient gold parting with silver and copper isotopes: implications from cementation experiments and for the analysis of gold artefacts
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Daniel Berger, Ernst Pernicka, Nicole Lockhoff, Gerhard Brügmann, and Michael Brauns
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Archeology ,Materials science ,Isotope ,Isotopes of copper ,Metallurgy ,Trace element ,chemistry.chemical_element ,Copper ,Gold parting ,Cementation process ,chemistry ,Refining ,Anthropology ,Cementation (metallurgy) - Abstract
Gold parting enabled the production of very pure gold for various purposes from the sixth century BC onwards, but analytical proof of this pyrotechnical process is difficult. We describe a new analytical approach for the identification of purified gold combining silver and copper isotopic with trace element analyses. Parting experiments were performed with gold-silver-copper alloys using the classical salt cementation process to investigate potential silver and copper isotope fractionation and changes in trace element concentrations. In addition, we provide the first comprehensive dataset of silver isotope ratios of archaeological gold objects from the Mediterranean and Central Europe to test whether or not gold refining can be identified on the basis of isotope systematics. The results show that very heavy silver and copper isotopic compositions are clear evidence for parted gold, but that the application of copper isotopes might be limited.
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- 2021
12. Reexamination of the N=50 and Z=28 shell closure
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X. Viñas, M. Centelles, Marta Anguiano, P. Bano, T. R. Routray, and L. M. Robledo
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Mass number ,Physics ,Mean field theory ,Proton ,Isotopes of copper ,Excited state ,Nuclear Theory ,Neutron ,Tensor ,Atomic physics ,Nuclear Experiment ,Ground state - Abstract
Recent experiments performed in neutron-rich copper isotopes have revealed a crossing in the nucleus $^{75}\mathrm{Cu}$ between the $3/{2}^{\ensuremath{-}}$ and $5/{2}^{\ensuremath{-}}$ levels, which correspond to the ground state and the first excited state in isotopes with mass number below $A=75$. Due to the strong single-particle character of these states, this scenario can be investigated through the analysis of the proton spectrum provided by mean-field models in nickel isotopes with neutron numbers between $N=40$ and $N=50$. In this work, we show that the aforementioned crossing is mainly driven by the mean field provided by the effective nucleon-nucleon and spin-orbit interactions. We also analyze the impact of the tensor interaction and find that in some mean-field models it is essential to reproduce the crossing of the $2{p}_{3/2}$ and $1{f}_{5/2}$ proton single-particle levels, as in the case of the SAMi-T Skyrme force and the D1M Gogny interaction, whereas in other cases, as for example the SLy5 Skyrme force, a reasonable tensor force appears to be unable to modify the mean-field enough to reproduce this level crossing. Finally, in the calculations performed with the so-called simple effective interaction (SEI), it is shown that the experimental data in nickel and copper isotopes considered in this work can be explained satisfactorily without any explicit consideration of the tensor interaction.
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- 2021
13. A copper isotope investigation of methane cycling in Late Archaean sediments
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R. C. J. Steele, Paul S. Savage, Natalya A.V. Zavina-James, Matthew R. Warke, Gareth Izon, Aubrey L. Zerkle, NERC, University of St Andrews. School of Earth & Environmental Sciences, University of St Andrews. St Andrews Centre for Exoplanet Science, and University of St Andrews. St Andrews Isotope Geochemistry
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010504 meteorology & atmospheric sciences ,Isotopes of copper ,Atmospheric evolution ,010502 geochemistry & geophysics ,01 natural sciences ,Methane ,Atmosphere ,chemistry.chemical_compound ,Geochemistry and Petrology ,Trace metal ,0105 earth and related environmental sciences ,GE ,Isotope ,Copper isotopes ,Great Oxygenation Event ,Geology ,DAS ,Archaean ,chemistry ,Aerobic methantrophy ,Environmental chemistry ,Anaerobic oxidation of methane ,Carbon dioxide ,Methane haze ,GE Environmental Sciences - Abstract
This research was supported by NERC award NE/L002590/1 to the IAPETUS DTP, and by NERC Standard Grant NE/J023485/2 to A.L.Z. The initiation of Cu isotope analysis at the University of St Andrews was aided significantly by a Carnegie Trust Research Incentive Grant awarded to P.S.S. The rise of oxygenic photosynthesis arguably represents the most important evolutionary step in Earth history. Recent studies, however, suggest that Earth’s pre-oxidative atmosphere was also heavily influenced by biological feedbacks. Most notably, recent geochemical records propose the existence of a hydrocarbon haze which periodically formed in response to enhanced biospheric methane fluxes. Copper isotopes provide a potential proxy for biological methane cycling; Cu is a bioessential trace metal and a key element in the aerobic oxidation of methane to carbon dioxide (methanotrophy). In addition, Cu isotopes are fractionated during biological uptake. Here, we present a high-resolution Cu isotope record measured in a suite of shales and carbonates from core GKF01, through the ~2.6–2.5 Ga Campbellrand-Malmani carbonate platform. Our data show a 0.85‰ range in Cu isotope composition and a negative excursion that predates the onset of a haze event. We interpret this excursion as representing a period of enhanced aerobic methane oxidation before the onset of the Great Oxidation Event. This places valuable time constraints on the evolution of this metabolism and firmly establishing Cu isotopes as a biomarker in Late Archaean rocks. Postprint
- Published
- 2021
14. RESEARCH ON COPPER-67 SEPARATION OBTAINED BY PHOTO-NUCLEAR FROM ZINC OF NATURAL COMPOSITION
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O.F. Stoyanov, O.I. Azarov, and V.O. Bocharov
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Nuclear reaction ,Materials science ,Ion exchange ,Isotopes of copper ,Coprecipitation ,Inorganic chemistry ,Extraction (chemistry) ,chemistry.chemical_element ,Zinc ,010403 inorganic & nuclear chemistry ,01 natural sciences ,Copper ,030218 nuclear medicine & medical imaging ,0104 chemical sciences ,Isotope separation ,law.invention ,03 medical and health sciences ,0302 clinical medicine ,chemistry ,law - Abstract
In the world, it is planned to produce promising for the manufacture of radiopharmaceuticals of radioisotope copper-67 by the reaction of its production from zinc-68 under the influence of γ-radiation on an electron accelerator. The next major issue is the separation of copper and zinc. Extraction, ion exchange and thermal distillation of zinc have already been studied in detail. Co-precipitation of copper with low zinc and thermal distillation of organic compounds of metals is promising.
- Published
- 2020
15. Cu and Zn isotope fractionation during oceanic alteration: Implications for Oceanic Cu and Zn cycles
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Ping-Ping Liu, Ze-Zhou Wang, Sheng-Ao Liu, Jingen Dai, and Yiwen Lv
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Goethite ,010504 meteorology & atmospheric sciences ,Isotope ,Chemistry ,Isotopes of copper ,Weathering ,010502 geochemistry & geophysics ,01 natural sciences ,Mantle (geology) ,Seafloor spreading ,Isotope fractionation ,Geochemistry and Petrology ,Environmental chemistry ,visual_art ,Isotopes of zinc ,visual_art.visual_art_medium ,0105 earth and related environmental sciences - Abstract
The behaviours of Cu, Zn and their isotopes during seafloor fluid-peridotite interaction and its influence on oceanic Cu-Zn cycles were investigated by analyzing a series of unaltered to strongly altered oceanic peridotites. Most of the altered peridotites have δ66Zn values indistinguishable from those of the unaltered ones (0.19 ± 0.05‰; 2SD), suggesting that seafloor alteration generally induces a small Zn isotope fractionation. A few altered samples that seem to have gained Zn have elevated δ66Zn, probably due to adsorption by ubiquitous secondary phases (e.g. goethite). Almost all altered peridotites show Cu loss (up to 90%) and have Cu isotope ratios that are shifted toward heavy values relative to the unaltered ones. Given that Cu is organically-complexed in fluids over a wide range of temperature and such fluids have strong preferences for the heavy isotopes, alteration and weathering alone are unlikely to account for the substantial loss of Cu coupled with elevated δ65Cu. An alternative mechanism is that initial Cu in peridotites was partly lost by alteration and weathering, and then Cu was added via adsorption by secondary mineral phases preferring the heavy Cu isotopes. This is confirmed by leaching experiments that were designed to extract the adsorbed Cu fractions in secondary phases. The results show that the leachates and the residua have, respectively, higher and lower δ65Cu values in comparison with the bulk peridotites, demonstrating that adsorption is an important mechanism for generating heavy copper isotope enrichments in the altered peridotites. In any case, mass balance considerations indicate that oceanic alteration must have resulted in a net input of isotopically light Cu from oceanic peridotites into the ocean. Recent estimates found that the Cu isotopic composition of the modern ocean is imbalanced, because all characterized sinks are isotopically light relative to characterized input fluxes, which requires an additional, isotopically light input. Our results indicate that seafloor alteration of abyssal peridotites is an isotopically light input (δ65Cu = −0.4‰ to −0.1‰) to the modern ocean, up to ∼1‰ lighter than the riverine input (∼0.7‰). First-order flux estimates suggest that this process exerts an important control on the marine budget of Cu. Most of Zn released during seafloor alteration has δ66Zn similar to that of mantle peridotites and this input is thus slightly lighter than the riverine input (∼0.33‰). Current estimates of modern oceanic Zn isotope cycles require consideration of this isotopically light source.
- Published
- 2019
16. Antibiotic treatment affects the expression levels of copper transporters and the isotopic composition of copper in the colon of mice
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Fernando A. Vicentini, Keith A. Sharkey, Kerri Miller, Michael E. Wieser, and Simon A. Hirota
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Male ,0301 basic medicine ,Colon ,Isotopes of copper ,ATP7A ,chemistry.chemical_element ,medicine.disease_cause ,digestive system ,01 natural sciences ,Cofactor ,Mice ,03 medical and health sciences ,Earth, Atmospheric, and Planetary Sciences ,Superoxide Dismutase-1 ,Isotopes ,In vivo ,microbiota ,medicine ,Animals ,copper isotopes ,skin and connective tissue diseases ,Cation Transport Proteins ,Copper Transporter 1 ,intestines ,Multidisciplinary ,biology ,Toxin ,010401 analytical chemistry ,CTR1 ,Transporter ,Biological Sciences ,Copper ,Anti-Bacterial Agents ,Gastrointestinal Microbiome ,0104 chemical sciences ,Mice, Inbred C57BL ,030104 developmental biology ,Biochemistry ,chemistry ,Copper-Transporting ATPases ,Physical Sciences ,biology.protein ,sense organs ,Applied Biological Sciences ,Intracellular - Abstract
Significance Isotopic analysis has the ability to detect changes in metal homeostasis in vivo. Using this advanced technique to investigate metal metabolism, we identified a significant change in copper processing in the gut of mice with depleted gut microbiota. In addition, we observed changes in the expression of copper transporters in the colon. The role of intestinal microbiota in copper processing in the gastrointestinal tract was previously unknown. Using the unique ability of isotopic analyses to detect changes in metal processing has enabled the identification of the intestinal microbiota as a significant influence on copper metabolism in the gut., Copper is a critical enzyme cofactor in the body but also a potent cellular toxin when intracellularly unbound. Thus, there is a delicate balance of intracellular copper, maintained by a series of complex interactions between the metal and specific copper transport and binding proteins. The gastrointestinal (GI) tract is the primary site of copper entry into the body and there has been considerable progress in understanding the intricacies of copper metabolism in this region. The GI tract is also host to diverse bacterial populations, and their role in copper metabolism is not well understood. In this study, we compared the isotopic fractionation of copper in the GI tract of mice with intestinal microbiota significantly depleted by antibiotic treatment to that in mice not receiving such treatment. We demonstrated variability in copper isotopic composition along the length of the gut. A significant difference, ∼1.0‰, in copper isotope abundances was measured in the proximal colon of antibiotic-treated mice. The changes in copper isotopic composition in the colon are accompanied by changes in copper transporters. Both CTR1, a copper importer, and ATP7A, a copper transporter across membranes, were significantly down-regulated in the colon of antibiotic-treated mice. This study demonstrated that isotope abundance measurements of metals can be used as an indicator of changes in metabolic processes in vivo. These measurements revealed a host–microbial interaction in the GI tract involved in the regulation of copper transport.
- Published
- 2019
17. Copper and zinc isotope variation of the VMS mineralization in the Kalatag district, eastern Tianshan, NW China
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Xi Chen, Li-Ya Yang, Ryan Mathur, Yan-Shuang Wu, Yao Li, Jun Xu, Xiaohua Deng, and Qi-Gui Mao
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chemistry.chemical_classification ,Stockwork ,Mineralization (geology) ,Sulfide ,Isotopes of copper ,Chalcopyrite ,Geochemistry ,chemistry.chemical_element ,010501 environmental sciences ,010502 geochemistry & geophysics ,01 natural sciences ,Copper ,chemistry ,Geochemistry and Petrology ,visual_art ,Isotopes of zinc ,Kinetic fractionation ,visual_art.visual_art_medium ,Economic Geology ,0105 earth and related environmental sciences - Abstract
The copper and zinc isotope ratios of massive sulfide and stockwork ores of Honghai volcanogenic massive sulfide (VMS) deposits in eastern Tianshan Orogen, NW China, were measured by multiple collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). The overall range of δ65Cu (where δ65Cu = [{(65Cu/63Cu)sample / (65Cu/63Cu)NIST976} − 1] × 1000) values of 16 mineral separates from Honghai deposit varies from −0.28 to 0.70‰, with near-surface massive Zn ores having isotopically heavy values compared to massive Cu ores from deeper levels. This suggests that a kinetic fractionation of copper isotopes could be encouraged during precipitation of chalcopyrite. However, the δ65Cu values of mineral separates from Massive Zn ores in drill hole ZK0302 are considerably higher than those of other mineral separates, which might be associated with the development of secondary mineralization. We also obtained zinc isotope data from 6 sphalerite-bearing samples. The range of δ66Zn (where δ66Zn = [(66Zn/64Zn)sample / (66Zn/64Zn)JMC 3-0749L − 1] × 1000) values varies from 0.05 to 0.17‰, with central parts of mineral separates having isotopically light values (δ66Zn = 0.05‰) compared with that from distal (δ66Zn = 0.12–0.17‰) of VMS system. The results suggest that Cu and Zn isotopes could provide a valuable tool for tracing flow paths toward the center of hydrothermal systems.
- Published
- 2019
18. Characterization of Four Copper Materials for Application as Reference Materials for High Precision Copper Isotope Analysis by Laser Ablation Inductively Coupled Plasma Multi-Collector Mass Spectrometry
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Simon E. Jackson, Zhaoping Yang, and Thomas Skulski
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Materials science ,Isotopes of copper ,Analytical chemistry ,LA-MC-ICP-MS ,chemistry.chemical_element ,010502 geochemistry & geophysics ,Mass spectrometry ,01 natural sciences ,lcsh:Chemistry ,Calibration ,copper isotopes ,native copper ,Original Research ,0105 earth and related environmental sciences ,Isotope ,Homogeneity (statistics) ,010401 analytical chemistry ,General Chemistry ,Copper ,reference materials ,0104 chemical sciences ,Chemistry ,homogeneity ,Certified reference materials ,lcsh:QD1-999 ,chemistry ,Inductively coupled plasma - Abstract
Laser ablation inductively coupled plasma multi-collector mass spectrometry (LA-MC-ICP-MS) allows rapid, in situ, highly precise measurements of Cu isotope ratios of native Cu and Cu-bearing minerals. However, the National Institute of Standards and Technology Cu-metal isotope standard NIST SRM976 that is commonly used to calibrate LA-MC-ICP-MS Cu isotope measurements of native Cu is no longer available. We have investigated the suitability of four Cu metal materials, SSC-1, SSC-3 and SSC-4 (cathode Cu metal rods) and CUPD-1 (Cu anode sawings), originally developed by the Canada Centre for Mineral and Energy Technology (CANMET) as certified reference materials for trace element analysis, as Cu isotope reference materials for LA-MC-ICP-MS analysis and solution nebulization (SN) of Cu. The Cu isotopic composition and homogeneity of these four materials were characterised by SN- and LA-MC-ICP-MS, and are reported for the first time. The bulk Cu isotopic compositions, expressed as δ65CuSRM976 in per mil (‰) relative to NIST SRM976 with combined uncertainties (U, k = 2), of SSC-1, SSC-3 and SSC-4, determined utilizing SN-MC-ICP-MS, are identical within analytical uncertainty at 0.03 ± 0.07‰ (n = 29), 0.04 ± 0.04‰ (n = 28), and 0.05 ± 0.08‰ (n = 29), respectively; the composition of CUPD-1 is 2.14 ± 0.08‰ (n = 28). The compositions are 0.01 ± 0.07‰ (n = 29), 0.04 ± 0.06‰ (n = 29), 0.03 ± 0.06‰ (n = 28) and 2.15 ± 0.06‰ (n = 28), respectively, relative to the European Reference Material ERM®-AE633 Cu isotope standard. The Cu isotope homogeneity of the four new reference materials was assessed by determining whether multiple individual in situ Cu isotope measurements made by LA-MC-ICP-MS analysis (43 µm spot size), using each of the other three reference materials as a calibrator, approximate a single normal distribution. We also investigate whether there are statistically significant differences between the mean δ65Cu values of three independent data sets for each of the Cu isotope reference materials using one-way analysis of variance (ANOVA). Normality tests (graphical assessment of normal distribution quantile-quantile plots, and the Shapiro-Wilk, Jarque-Bera and reduced chi-squared statistic tests) show that: 1) the Cu isotope data acquired on SSC-1, SSC-3, SSC-4 and CUPD-1 do not depart significantly from a normal distribution, 2) the scatter of the Cu isotope data is due to analytical uncertainty with 95% confidence, and 3) there are no other significant sources of scatter; e.g. heterogeneity of the reference materials. The results of one-way ANOVA reveal that the mean difference of the δ65Cu value for each of the reference materials SSC-1, SSC-3, SSC-4 and CUPD-1 is statistically not significant at the 0.05 level. The mean δ65CuSRM976 values with combined uncertainties (U, k = 2) of SSC-1, SSC-3, SSC-4 and CUPD-1, determined by LA-MC-ICP-MS using each of the other three reference materials as a calibration standard, are 0.03 ± 0.09‰ (n = 132), 0.05 ± 0.09‰ (n = 154), 0.03 ± 0.09‰ (n = 144) and 2.14 ± 0.10‰ (n = 106), respectively. These values are in agreement with those determined by SN-MC-ICP-MS analysis at the 95% confidence level and have excellent precision (2 s.d. ≤ 0.10‰). These results suggest that SSC-1, SSC-3, SSC-4 and CUPD-1 can be considered isotopically homogeneous at a spatial resolution of 43 μm, and they are suitable reference materials for calibration and quality control of in situ and solution nebulization Cu isotope analyses of Cu.
- Published
- 2021
19. Copper isotope systematics in seafloor hydrothermal systems: A case study of TAG and Snake Pit fields, Mid-Atlantic Ridge
- Author
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Ewan Pelleter, Olivier Rouxel, Marie Anne Cambon, Lucie Pastor, Yoan Germain, Laetitia Leroy, Florian Besson, Sandrine Cheron, Audrey Boissier, Cecile Cathalot, and Yannick Djedjroh
- Subjects
Systematics ,Isotopes of copper ,Geochemistry ,Mid-Atlantic Ridge ,Seafloor spreading ,Hydrothermal circulation ,Geology - Published
- 2021
20. Copper isotope evidence of particulate shuttle dynamics in the Late Pennsylvanian North American Midcontinent Sea, with implications for glacio-eustatic magnitude
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Lian Zhou, Yu Jiao, and Jinhua Liu
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Paleontology ,Isotopes of copper ,Magnitude (astronomy) ,Pennsylvanian ,Particulates ,Geology - Published
- 2021
21. Copper Isotope Fractionation by Diffusion in Basaltic Melts
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Anat Shahar, Peng Ni, and Youxue Zhang
- Subjects
Basalt ,Chemistry ,Isotopes of copper ,Analytical chemistry ,Fractionation ,Diffusion (business) - Published
- 2021
22. Geomedical application of copper isotope ratios: change of δ65Cu in xenograft model of human cancers
- Author
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Lívia Varga, Gergely Rácz, Gabriella Kiss, Ildikó Krencz, László Palcsu, Csaba Szabó, Enikő Vetlényi, and Titanilla Dankó
- Subjects
Chemistry ,Isotopes of copper ,Radiochemistry - Abstract
In geosciences, high precision isotope ratio determination provides essential information about processes in geological systems. Novel ambitions evolve closer to biological applications. Copper is an essential metal for human body taking part of several cellular processes (e.g. respiratory chain, enzyme function, iron metabolism, elimination of reactive oxygen species, cell signalling pathways etc). However, the disorder of copper homeostasis causes serious diseases like Wilson disease (Cu accumulation in liver caused by genetical disorder) and it could also promote tumour growth by supporting angiogenesis and metastasis formation [Denoyer et al., 2015]. Despite numerous experiments, focusing on copper concentration determination in different tumour tissues (e.g. breast, lung cancer, etc.) hoping to assist in tumour diagnosis, the results are not convincing enough. However, previous studies on hepatocellular cancer and oral squamous cell carcinoma showed that tumour tissue appears to be relatively enriched in 65Cu compared to normal tissue whereas the δ65Cu in blood of tumorous patient decreased according to data obtained from control population [Balter et al., 2015, Lobo et al., 2017]. Our main aim is to elaborate a method to understand better the change in 63Cu/65Cu stable isotope ratio during tumour growth. In this approach, we present our first results on copper isotope ratio determination in a xenograft mouse model. Our model was established in SCID (severe combined immunodeficiency disease) mice by injecting human cancer cells (1x107 cells) subcutaneously. After the tumour reached approximately 2-3 cm diameter, the tumour mass was cut it in small, equal pieces and transplanted further into 10 mice increasing the experimental set-up homogeneity. All the animals were sacrificed by cardiac puncture under deep terminal anaesthesia within four weeks. Tumour and organs were removed by ceramic knife then were frozen with liquid nitrogen and stored at -80°C. We measured the copper concentration and δ65Cu in the tumour tissue, blood, liver, kidney and brain. A clean laboratory ambience was chosen to perform the sample preparation processes decreasing the environmental contamination. Separation of copper from other biologically essential element (Na, Mg, Fe, Zn) interfering the copper isotope measurement is a serious condition of the preparation [Lauwens et al., 2017]. Effects of sodium (23Na40Ar+) and magnesium (25Mg40Ar+) on copper isotope ratio were solved by choosing not the peak center but the interference-free plateau. Our measurements have been carried out on a Thermo Neptune PLUS multicollector mass spectrometer equipped with 9 moveable Faraday detectors, 3 amplifiers with a resistance of 1013 Ohm, and 6 amplifiers with a resistance of 1011 Ohm, in wet plasma conditions. The mass spectrometric measurement of the copper isotope ratio is doped either with Ni or Ga reference material which have a well-known isotope ratios. References:Balter V. et al. PNAS 2015; 112: 982−985.Denoyer D. et al. Metallomics 2015; 7: 1459−76.Lauwens S. et al. J. Anal. At. Spectrom. 2017; 32: 597−608.Lobo L. et al. Talanta 2017; 165: 92−97.
- Published
- 2020
23. Author response for 'EVALUATING COPPER ISOTOPE FRACTIONATION IN THE METALLURGICAL OPERATIONAL CHAIN: AN EXPERIMENTAL APPROACH'
- Author
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S. Klein and T. Rose
- Subjects
Chain (algebraic topology) ,Isotopes of copper ,Chemistry ,Metallurgy ,Fractionation - Published
- 2020
24. Specific criteria for BCS-type cuprate superconductivity and peculiar isotope effects on the critical superconducting transition temperature
- Author
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B L Oksengendler, Sh.S. Djumanov, and S. Dzhumanov
- Subjects
Condensed Matter::Quantum Gases ,Superconductivity ,Physics ,Condensed matter physics ,010308 nuclear & particles physics ,Isotopes of copper ,General Physics and Astronomy ,Fermi energy ,Type (model theory) ,01 natural sciences ,010305 fluids & plasmas ,Condensed Matter::Superconductivity ,Pairing ,0103 physical sciences ,Kinetic isotope effect ,Condensed Matter::Strongly Correlated Electrons ,Cuprate ,Energy (signal processing) - Abstract
So far, many researchers have been misled to believe that the Bardeen–Cooper–Schrieffer (BCS)-like (s- or d-wave) pairing theory is adequate for explaining high- $$T_\mathrm {c}$$ superconductivity in doped cuprates from underdoped to overdoped regime. We show that the doped cuprates, depending on the Fermi energy ( $$\varepsilon _\mathrm {F}$$ ) and the energy ( $$\varepsilon _\mathrm {A}$$ ) of the effective attraction between pairing carriers, might be either unconventional (non-BCS-type) superconductors (at intermediate doping) or BCS-type superconductors (at higher doping). We argue that specific criteria for BCS-type superconductivity formulated in terms of two ratios $$\varepsilon _\mathrm {A}/\varepsilon _\mathrm {F}$$ and $$\Delta /\varepsilon _\mathrm {F}$$ (where $$\Delta $$ is the BCS-like gap) must be met in these systems. We demonstrate that these criteria are satisfied only in overdoped cuprates but not in underdoped and optimally doped cuprates, where the origin of high- $$T_\mathrm {c}$$ superconductivity is quite different from the BCS-type (s- or d-wave) superconductivity. The BCS-like pairing theory is then used to calculate the critical superconducting transition temperature ( $$T_\mathrm {c}$$ ) and the peculiar oxygen and copper isotope effects on $$T_\mathrm {c}$$ in overdoped cuprates.
- Published
- 2019
25. Absolute Isotopic Abundance Ratios and the Atomic Weight of a Reference Sample of Chromium
- Author
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Edward J. Catanzaro, William R. Shields, Ernest L. Garner, and T. J. Murphy
- Subjects
Mass number ,Strontium ,Isotopes of copper ,Chemistry ,Analytical chemistry ,chemistry.chemical_element ,Thermal ionization ,Natural abundance ,Mass spectrometry ,Atomic mass ,Isotopes of strontium ,Physics and Chemistry - Abstract
Absolute values have been obtained for the isotopic abundance ratios of a reference sample of strontium using solid sample thermal ionization mass speelrometry. Samples of independently known isotopic composition prepared from chemically pure and nearly isotopically pure separated strontium isotopes were used to calibrate the mass speelrometry. The resulting absolute 88Sr/86Sr, 87Sr/86Sr, and 84Sr/86Sr ratios are 8.3786 ± 0.0033, 0.71034 ± 0.00026, and 0.05655 ± 0.00014 respectively which yields atom percents of: 88Sr = 82.5845 ± 0.0066, 87Sr = 7.0015 ± 0.0026, 86Sr = 9.8566 ± 0.0034. and 81Sr = 0.5574 ± 0.0015. The atomie weight calculated from these abundances is 87.61681 ± 0.00012. The indicated uncertainties are overall limits of error based on 95 percent confidence limits for the mean and allowances for the effects of possible systematic error.
- Published
- 2019
26. Volatile distributions in and on the Moon revealed by Cu and Fe isotopes in the ‘Rusty Rock’ 66095
- Author
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James M.D. Day, Charles K. Shearer, Frédéric Moynier, Paolo A. Sossi, Scripps Institution of Oceanography (SIO), University of California [San Diego] (UC San Diego), University of California-University of California, Institut de Physique du Globe de Paris (IPGP), Institut national des sciences de l'Univers (INSU - CNRS)-IPG PARIS-Université de La Réunion (UR)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Univ New Mexico, Inst Meteorit, Albuquerque, NM 87131 USA, Inst Univ France, F-75005 Paris, France, and NASA Emerging Worlds program NNX15AL74GEuropean Research Council under the H2020 framework program/ERC grant 637503UnivEarthS Labex program at Sorbonne Paris Cite ANR-10-LABX-0023ANR-11-IDEX-0005-02French National Research Agency (ANR) IPGP
- Subjects
Basalt ,010504 meteorology & atmospheric sciences ,Isotope ,Chemistry ,Isotopes of copper ,Copper isotopes ,Lunar mare ,Condensation ,Evaporation ,Analytical chemistry ,Iron isotopes ,Volatile elements ,010502 geochemistry & geophysics ,01 natural sciences ,Outgassing ,Condensates ,13. Climate action ,Geochemistry and Petrology ,[SDU]Sciences of the Universe [physics] ,Breccia ,Moon ,Volatiles ,ComputingMilieux_MISCELLANEOUS ,0105 earth and related environmental sciences ,Rusty Rock - Abstract
The Apollo 16 ‘Rusty Rock’ impact melt breccia 66095 is a volatile-rich sample, with the volatiles inherited through vapor condensation from an internal lunar source formed during thermo-magmatic evolution of the Moon. We report Cu and Fe isotope data for 66095 and find that bulk-rocks, residues and acid leaches span a relatively limited range of compositions (3.0 ± 1.3 wt.% FeO [range = 2.0–4.8 wt.%], 5.4 ± 3.1 ppm Cu [range = 3–12 ppm], average δ56Fe of 0.15 ± 0.05‰ [weighted mean = 0.156‰] and δ65Cu of 0.72 ± 0.14‰ [weighted mean = 0.78‰]). In contrast to the extreme enrichment of the light isotopes of Zn and heavy isotopes of Cl in 66095, δ65Cu and δ56Fe in the sample lie within the previously reported range for lunar mare basalts (0.92 ± 0.16‰ and 0.12 ± 0.02‰, respectively). The lack of extreme isotopic fractionation for Cu and Fe isotopes reflects compositions inherent to 66095, with condensation of a cooling gas from impact-generated fumarolic activity at temperatures too low to lead to the condensation of Cu and Fe in the sample, but higher than required to condense Zn. Together with thermodynamic models, these constraints suggest that the gas condensed within 66095 between 700 and 900 °C (assuming a pressure of 10−6 and an fO2 of IW-2). That the Cu and Fe isotopic compositions of sample 66095 are within the range of mare basalts removes the need for an exotic, volatile-enriched source. The enrichment in Tl, Br, Cd, Sn, Zn, Pb, Rb, Cs, Ga, B, Cl, Li relative to Bi, Se, Te, Ge, Cu, Ag, Sb, Mn, P, Cr and Fe in the ‘Rusty Rock’ is consistent with volcanic outgassing models and indicates that 66095 likely formed distal from the original source of the gas. The volatile-rich character of 66095 is consistent with impact-generated fumarolic activity in the region of the Cayley Plains, demonstrating that volatile-rich rocks can occur on the lunar surface from outgassing of a volatile-poor lunar interior. The ‘Rusty Rock’ indicates that the lunar interior is significantly depleted in volatile elements and compounds and that volatile-rich surface rocks likely formed through vapor condensation. Remote sensing studies have detected volatiles on the lunar surface, attributing them dominantly to solar wind. Based on the ‘Rusty Rock’, some of these surface volatiles may also originate from the Moon’s interior.
- Published
- 2019
27. A critical evaluation of copper isotopes in Precambrian Iron Formations as a paleoceanographic proxy
- Author
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Fanny Thibon, Harilaos Tsikos, John Foden, Francis Albarède, Janne Blichert-Toft, Laboratoire de Géologie de Lyon - Terre, Planètes, Environnement [Lyon] (LGL-TPE), Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon), Laboratoire de Sciences de la Terre (LST), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Rhodes University, Grahamstown, Laboratoire de Géologie de Lyon - Terre, Planètes, Environnement (LGL-TPE), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut national des sciences de l'Univers (INSU - CNRS)-Université Jean Monnet - Saint-Étienne (UJM)-Centre National de la Recherche Scientifique (CNRS)
- Subjects
010504 meteorology & atmospheric sciences ,Isotope ,Isotopes of copper ,Great Oxygenation Event ,Iron oxide ,Geochemistry ,chemistry.chemical_element ,Crust ,010502 geochemistry & geophysics ,01 natural sciences ,Copper ,chemistry.chemical_compound ,Precambrian ,Isotope fractionation ,chemistry ,13. Climate action ,Geochemistry and Petrology ,[SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry ,Geology ,ComputingMilieux_MISCELLANEOUS ,0105 earth and related environmental sciences - Abstract
Trace metals in Iron Formations (IF) have been widely used as proxies for oceanic redox processes and oxygen evolution leading to the Great Oxidation Event (GOE). Copper has hitherto received comparatively little attention, with a single study reporting variation in δ65Cu between pre- and post-GOE black shales. This is attributed to postulated isotope fractionation effects in the pre-GOE ocean during widespread iron oxide deposition in IF. Here we focus on the application of Cu isotopes in two classic IF-containing sequences of the Neoarchean-Paleoproterozoic, namely the Hamersley (Australia) and Transvaal (South Africa) Supergroups. We specifically targeted the oxide-rich Joffre and Kuruman IF, the carbonate-rich Griquatown IF, and the Mn-rich Hotazel IF, which collectively record over 100 Ma of sustained IF deposition in the pre-GOE ocean. The aim was to assess the utility of Cu isotopes in IF as a paleoceanographic proxy in view of existing oxygen evolution models. Iron formation Cu concentrations are low compared to average crust and modern oceanic Fe-Mn oxide deposits, with average values between 1 and 5 ppm for all four IF data sets. Copper concentrations show no systematic variability with mineralogy, no statistical correlation with bulk Fe and Mn contents, good correlations with Ti (rCu-Ti = 0.73) for the Joffre data set and with Cr, Ni, and V for the South African data sets, and shale-like Cu/Ti ratios. Isotopic results show statistically invariant average δ65Cu values very close to 0‰ for all but the Joffre IF which has a marginally negative average δ65Cu value (−0.24 ± 0.22‰). Combined with other trace transition metal systematics, the Cu isotope data point to a Cu source that was controlled largely by inputs of fine volcanic-derived particles (ash), thus placing limitations on its utility as a paleoceanographic redox proxy during IF genesis.
- Published
- 2019
28. Origins of Chalcocite Defined by Copper Isotope Values
- Author
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Marc Wilson, Ryan Mathur, H. Falck, J. Milton, E. Belogub, A. Rose, and Wayne Powell
- Subjects
Chalcocite ,Article Subject ,010504 meteorology & atmospheric sciences ,Chemistry ,Isotopes of copper ,lcsh:QE1-996.5 ,Inorganic chemistry ,engineering.material ,010502 geochemistry & geophysics ,01 natural sciences ,lcsh:Geology ,engineering ,General Earth and Planetary Sciences ,0105 earth and related environmental sciences - Abstract
The origin of chalcocite is explored through a comparison of the copper isotope values of this mineral from supergene enrichment, sedimentary copper/red bed, and high-temperature hypogene mineralization around the world. Data from the literature and the data presented here (n=361) reveal that chalcocite from high-temperature mineralization has the tightest cluster of values of δCu65=0±0.6 in comparison to sedimentary copper/red bed δCu65=-0.9±1.0 and supergene enrichment δCu65=+1.9±1.8. Although the errors of the means overlap, large portions of the data lie in different values, allowing for distinguishing ranges for δCu65 of ‰ for sedimentary copper/red bed, between -1 and +1 for high-temperature hypogene, and >+1 for supergene enrichment chalcocite. The copper isotope values of sedimentary copper/red bed and supergene enrichment chalcocite are caused by redox reactions associated with the dissolution and transport of copper, whereas the tighter range of copper isotope values for hypogene minerals is associated with processes active with equilibrium conditions.
- Published
- 2018
29. Digging deeper: Insights into metallurgical transitions in European prehistory through copper isotopes
- Author
-
Ryan Mathur, H. Arthur Bankoff, Vojislav Filipovic, Linda Godfrey, Wayne Powell, Andrea Mason, and Aleksandar Bulatovic
- Subjects
010506 paleontology ,Archeology ,060102 archaeology ,Isotopes of copper ,Metallurgy ,chemistry.chemical_element ,06 humanities and the arts ,Chalcolithic ,Hiatus ,01 natural sciences ,Copper ,Sedimentary depositional environment ,Prehistory ,chemistry ,Bronze Age ,Smelting ,0601 history and archaeology ,Geology ,0105 earth and related environmental sciences - Abstract
Southeastern Europe is the birthplace of metallurgy, with evidence of copper smelting at ca. 5000 BCE. There the later Eneolithic (Copper Age) was associated with the casting of massive copper tools. However, copper metallurgy in this region ceased, or significantly decreased, centuries before the dawn of the Bronze Age. Archaeologists continue to be debate whether this hiatus was imposed on early metalworking communities as a result of exhaustion of workable mineral resources, or instead a cultural transition that was associated with changes in depositional practices and material culture. Copper isotopes provide a broadly applicable means of addressing this question. Copper isotopes fractionate in the near-surface environment such that surficial oxide ores can be differentiated from non-weathered sulphide ores that occur at greater depth. This compositional variation is transferred to associated copper artifacts, the final product of the metallurgical process. In the central Balkans, a shift from 65Cu-enriched to 65Cu-depleted copper artifacts occurs across the metallurgical hiatus at the Eneolithic-Bronze Age boundary, ca. 2500 BCE. This indicates that the reemergence of metal production at the beginning of the Bronze Age is associated with pyrotechnical advancements that allowed for the extraction of copper from sulphide ore. Thus copper isotopes provide direct evidence that the copper hiatus was the result of exhaustion of near-surface oxide ores after one-and-a-half millennia of mining, and that the beginning of the Bronze Age in the Balkans is associated with the introduction of more complex smelting techniques for metal extraction from regionally abundant sulphidic deposits.
- Published
- 2017
30. Copper isotope signatures in modern marine sediments
- Author
-
Timothy W. Lyons, Derek Vance, Susan H. Little, James McManus, Silke Severmann, and Leverhulme Trust
- Subjects
Oceanic mass balance ,010504 meteorology & atmospheric sciences ,Isotope ,Copper isotopes ,Stable isotope ratio ,Isotopes of copper ,Mineralogy ,Sediment ,010502 geochemistry & geophysics ,01 natural sciences ,Organic ligands ,Isotope fractionation ,0403 Geology ,Geochemistry and Petrology ,Paleoceanography ,Environmental chemistry ,Black shales ,0402 Geochemistry ,Seawater ,Dissolution ,Geology ,0105 earth and related environmental sciences - Abstract
Geochimica et Cosmochimica Acta, 212, ISSN:0016-7037, ISSN:1872-9533
- Published
- 2017
31. Copper isotopes trace the evolution of skarn ores: A case study from the Hongshan-Hongniu Cu deposit, southwest China
- Author
-
Xuefeng Li, Peng Wang, Kairan Liu, Guochen Dong, and M. Santosh
- Subjects
Mineralization (geology) ,010504 meteorology & atmospheric sciences ,Isotope ,Hypogene ,Chalcopyrite ,Isotopes of copper ,Geochemistry ,Quartz monzonite ,Geology ,Skarn ,010502 geochemistry & geophysics ,01 natural sciences ,Ore genesis ,Geochemistry and Petrology ,visual_art ,visual_art.visual_art_medium ,Economic Geology ,0105 earth and related environmental sciences - Abstract
Transition metal isotopes are sensitive geochemical tracers of ore genesis. Here we present MC-ICP-MS analytical data of Cu isotope compositions from the Hongshan-Hongniu Cu deposit in Yunnan province. The δ 65 Cu values (δ 65 Cu = [( 65 Cu/ 63 Cu) sample /( 65 Cu/ 63 Cu) NIST976 − 1] × 1000) of seven whole-rock quartz monzonite porphyries and twenty-two chalcopyrite samples from the skarn ore-bodies display relatively narrow ranges from −0.15‰ to 0.38‰ and from −0.02‰ to 0.77‰, respectively. The overlap of δ 65 Cu values indicates a genetic relationship between the quartz monzonite porphyry and skarn ore-bodies. We also evaluate the spatial and temporal variations of Cu isotope compositions in the skarn ore-bodies by comparison with some well-documented porphyry deposits in the world. The quartz monzonite porphyry shows compositional zoning with the inner domain enriched in heavy Cu isotope and the skarn related to the porphyry depleted in heavy Cu isotope. The chalcopyrites that formed during the late stage of mineralization tend to be enriched in heavy Cu isotope, and this feature is analogous to porphyry deposits. The δ 65 Cu values of the quartz monzonite porphyry show typical features of hypogene mineralization, suggesting a potential scope for deep exploration and development in this deposit.
- Published
- 2017
32. Copper isotopic compositions of the Zijinshan high-sulfidation epithermal Cu–Au deposit, South China: Implications for deposit origin
- Author
-
Sheng-Ao Liu, Ruizhong Hu, Xiaofeng Li, Yongyong Tang, Li-Yan Wu, and Yanwen Tang
- Subjects
Mineral ,010504 meteorology & atmospheric sciences ,Hypogene ,Isotopes of copper ,Sulfidation ,Geochemistry ,chemistry.chemical_element ,Mineralogy ,Geology ,engineering.material ,010502 geochemistry & geophysics ,Digenite ,Alunite ,01 natural sciences ,Copper ,Isotopic signature ,chemistry ,Geochemistry and Petrology ,engineering ,Economic Geology ,0105 earth and related environmental sciences - Abstract
The Zijinshan high-sulfidation epithermal Cu–Au deposit is located in the Zijinshan ore field of South China, comprising porphyry–epithermal Cu–Au–Mo–Ag ore systems. The Cu ore body is more than 1000 m thick and is characterized by an assemblage of digenite–covellite–enargite–alunite. Digenite is the dominant Cu-bearing mineral, which makes this deposit unique, although the mechanisms of digenite formation remain controversial. To elucidate the genesis of digenite, this paper presents the Cu isotopic compositions of Cu-sulfides in the Zijinshan high-sulfidation Cu–Au deposit. The Cu isotopic values (65Cu relative to NIST 976) of all samples range from −2.97‰ to +0.34‰, and most values fall in a narrow range from −0.49‰ to +0.34‰, which is similar to the Cu isotopic signature of typical porphyry systems. Copper isotope ratios of each mineral decrease with increasing depth, a trend that is also typical of porphyry deposits. The variation tendency of δ65Cu values between sulfides is consistent with the sequence of mineral formation. These observations suggest that the Cu-sulfides in the Zijinshan Cu–Au deposit have a hypogene origin.
- Published
- 2017
33. The potential of stable Cu isotopes for the identification of Bronze Age ore mineral sources from Cyprus and Faynan: results from Uluburun and Khirbat Hamra Ifdan
- Author
-
Andreas Hauptmann, Hans-Michael Seitz, Sabine Klein, and Moritz Jansen
- Subjects
010506 paleontology ,Archeology ,060102 archaeology ,Isotope ,Isotopes of copper ,Hypogene ,Metallurgy ,chemistry.chemical_element ,06 humanities and the arts ,01 natural sciences ,Copper ,Prehistory ,chemistry ,Bronze Age ,Anthropology ,Smelting ,0601 history and archaeology ,Mineral Sources ,Geology ,0105 earth and related environmental sciences - Abstract
Copper isotope ratios differ between hypogene sulfidic, supergene sulfidic and oxidized ore sources. Traditional lead isotope signatures of ancient metals are specific to deposits, while Cu isotope signatures are specific to the types of ore minerals used for metal production in ancient times. Two methodological case studies are presented: First, the mining district of Faynan (Jordan) was investigated. Here, mainly oxidized copper ores occur in the deposits. The production of copper from Fayan’s ore sources is confirmed by the measurement of the Cu isotope signature of ingots from the Early Bronze Age metal workshop from Khirbat Hamra Ifdan. Based on our results illustrating differences in the Cu isotope composition between the ore mineralizations from Timna (Israel) and Faynan, it is now possible to determine these prehistoric mining districts from which copper artifacts originated by combining trace elements and Pb isotopes with Cu isotopes. The second case study presents data on Late Bronze Age copper production in Cyprus. Oxhide ingots from the shipwreck of Uluburun (Turkey) were tested for their lead isotope signatures and assigned to Cypriot deposits in the recent decades. The oxhide ingots from Uluburun show a Cu isotope signature which we also found for oxidized copper ores from Cyprus, while younger oxhide ingots as well as metallurgical slag from the Cypriot settlements Kition and Enkomi show a different signature which might be due to the use of sulfidic ore sources from a greater depth of deposits. We assert that there could be a chronological shift from oxidized to sulfidic ore sources for the copper production in Cyprus, requiring different technologies. Therefore, Cu isotopes can be used as a proxy to reconstruct mining and induced smelting activities in ancient times.
- Published
- 2017
34. Computational modelling of the redistribution of copper isotopes by proteins in the liver
- Author
-
Arvi Rauk, Alexander Tennant, and Michael E. Wieser
- Subjects
0301 basic medicine ,Isotopes of copper ,Biophysics ,Analytical chemistry ,chemistry.chemical_element ,Fractionation ,010402 general chemistry ,01 natural sciences ,Biochemistry ,Biomaterials ,03 medical and health sciences ,Blood serum ,Humans ,Computer Simulation ,Cation Transport Proteins ,Copper Transporter 1 ,Chromatography ,biology ,Isotope ,Stable isotope ratio ,Chemistry ,Metals and Alloys ,Ceruloplasmin ,Copper ,Equilibrium fractionation ,0104 chemical sciences ,030104 developmental biology ,Copper Radioisotopes ,Liver ,Chemistry (miscellaneous) ,biology.protein - Abstract
Changes in the stable isotope composition of copper in blood serum as a result of biological processes in the liver were quantified as coupled equilibrium fractionation processes. The model used calculated reduced partition function ratios corresponding to interactions involving individual proteins using Density Functional Theory. This quantified the effect that each process had on the redistribution of copper isotopes in the liver. It was not possible to calculate the reduced partition function of CTR1 as a high resolution crystal structure of its copper binding domains are unavailable at the time of writing, and an optimization process was used to estimate the reduced partition function of CTR1 and constrain the possible isotopic fractionation associated with interactions involving CTR1 independent of direct DFT calculations and assumptions of its structure. The exchange of copper between ceruloplasmin and ATP7B has the most significant impact on the copper isotopic composition of blood serum. The model calculation for the isotopic composition of ceruloplasmin and albumin are δ65Cu = (-0.54 ± 0.10)‰ and δ65Cu = (0.08 ± 0.25)‰ respectively, assuming that serum is 90% ceruloplasmin and 10% albumin using a measured δ65Cu of serum of (0.52 ± 0.08)‰. The model also predicts that the isotopic composition of the tri-nuclear binding motif of ceruloplasmin may be relatively depleted in the lighter isotope of Cu compared to the other copper binding sites by as much as -1.08 ± 0.45‰.
- Published
- 2017
35. Development of Copper Isotope Reference Materials for High Precision Copper Isotope Analysis by Laser Ablation Inductively Coupled Multi-collector Mass Spectrometry
- Author
-
Tom Skulski, Zhaoping Yang, and Simon E. Jackson
- Subjects
Materials science ,Laser ablation ,Isotopes of copper ,Radiochemistry ,Mass spectrometry ,Instrumentation - Published
- 2020
36. Copper Isotope Measurements Using a Neptune MC-ICP-MS
- Author
-
Ryu, Jong-Sik, Sanghee Park, Kil, Youngwoo, and Shin Hyung Seon
- Subjects
010504 meteorology & atmospheric sciences ,chemistry ,Mc icp ms ,Isotopes of copper ,Neptune ,Radiochemistry ,chemistry.chemical_element ,010502 geochemistry & geophysics ,01 natural sciences ,Copper ,0105 earth and related environmental sciences - Published
- 2016
37. Copper and zinc isotope fractionation during deposition and weathering of highly metalliferous black shales in central China
- Author
-
Sheng-Ao Liu, Jian-Ming Zhu, Yiwen Lv, and Shuguang Li
- Subjects
chemistry.chemical_classification ,010504 meteorology & atmospheric sciences ,Sulfide ,Isotopes of copper ,Stable isotope ratio ,Geochemistry ,Geology ,Weathering ,010502 geochemistry & geophysics ,01 natural sciences ,Isotope fractionation ,chemistry ,Geochemistry and Petrology ,Isotopes of zinc ,Organic matter ,Oil shale ,0105 earth and related environmental sciences - Abstract
Black shales represent one of the main reservoirs of metals released to hydrosphere via chemical weathering and play an important role in geochemical cycling of metals in the ocean. The stable isotope systematics of transitional metals (e.g., Cu and Zn) may be used as a proxy for evaluating their geochemical cycling. To investigate the behaviors of Cu and Zn isotopes during metal enrichment of black shales and the migration during weathering, in this study we reported Cu and Zn concentration and isotope data for unweathered and weathered metalliferous shales and siliceous interbeds from the Maokou Formation in central China. The unweathered shales and cherts have moderately enriched Cu and Zn concentrations with silicate-like δ 65 Cu (+ 0.14 ± 0.09‰, 1σ) but heavy δ 66 Zn (0.51 ± 0.11‰, 1σ). The elevated δ 66 Zn values reflect an important contribution from seawater via sulfide precipitation and/or organic matter (OM) adsorption. The Zn isotopic compositions of these metalliferous shales are different from those of the ‘normal’ shales, highlighting the potential of Zn isotopes as a tracer for metal enrichment in natural systems. The weathered shales and cherts have an extreme δ 65 Cu range from − 6.42‰ to + 19.73‰ and a modest δ 66 Zn range of + 0.25‰ to + 0.78‰. The strongly weathered samples have lower Cu and Zn concentrations and lighter isotopic compositions compared to the weakly weathered samples. The leaching of Cu- and Zn-rich sulfides in shallow depths and their downward transport and refixation by Fe-sulfide account for the Cu and Zn isotope fractionation, with the huge Cu isotope variation generated by multistage redox leaching. In general, δ 66 Zn values of the weathered shales shift towards light values compared to the unweathered protoliths, suggesting that shale weathering releases Zn which is isotopically heavier than igneous rocks and the global riverine average (+ 0.33‰). Our results therefore indicate that Cu isotopes can be extremely fractionated during weathering of Cu-rich shales and both heavy Cu and Zn isotopes are preferentially released into fluids during shale weathering. These results should be considered when evaluating geochemical cycling of Cu and Zn in the modern or past oceans.
- Published
- 2016
38. Review for 'EVALUATING COPPER ISOTOPE FRACTIONATION IN THE METALLURGICAL OPERATIONAL CHAIN: AN EXPERIMENTAL APPROACH'
- Author
-
Ryan Mathur
- Subjects
Chain (algebraic topology) ,Isotopes of copper ,Chemistry ,Metallurgy ,Fractionation - Published
- 2019
39. Copper Isotope Compositions of Superoxide Dismutase and Metallothionein from Post-Mortem Human Frontal Cortex
- Author
-
Fiona Larner, Catriona McLean, Blaine R. Roberts, and Alex N. Halliday
- Subjects
0301 basic medicine ,Isotopes of copper ,chemistry.chemical_element ,01 natural sciences ,Inorganic Chemistry ,Superoxide dismutase ,03 medical and health sciences ,Blood serum ,Isotope fractionation ,MCICPMS ,lcsh:Inorganic chemistry ,Metallothionein ,biology ,Isotope ,Stable isotope ratio ,010401 analytical chemistry ,Radiochemistry ,metallothionein ,Copper ,superoxide dismutase ,lcsh:QD146-197 ,0104 chemical sciences ,3. Good health ,030104 developmental biology ,chemistry ,copper ,biology.protein ,isotope fractionation ,Alzheimer’s disease - Abstract
The natural copper isotopic compositions of superoxide dismutase and metallothionein from six post-mortem human frontal cortices were determined using a combination of size exclusion protein liquid chromatography, followed by anion exchange chromatography and multiple collector inductively-coupled plasma mass spectrometry. Superoxide dismutase was enriched in the heavier 65Cu relative to the metallothionein fraction in all specimen pairs. The isotopic compositions were independent of copper content. This finding provides evidence that nitrogen ligands in protein copper binding sites will be enriched in heavy metal isotopes, and sulphur ligands will preferentially incorporate lighter isotopes in vivo. This in turn has implications for understanding isotopic distributions within different components in the body and the dominant ligands in different tissues. Differences in Cu isotope distributions between the two proteins were seen between Alzheimer&rsquo, s disease and healthy control samples, when normalised for sex.
- Published
- 2019
40. Copper isotope fractionation during excretion from a phototrophic biofilm
- Author
-
Jérôme Viers, J. L. Rols, Margot Coutaud, Merlin Méheut, Oleg S. Pokrovsky, Géosciences Environnement Toulouse (GET), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Observatoire Midi-Pyrénées (OMP), Météo France-Centre National d'Études Spatiales [Toulouse] (CNES)-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Météo France-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Laboratoire Ecologie Fonctionnelle et Environnement (ECOLAB), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Observatoire Midi-Pyrénées (OMP), Météo France-Centre National d'Études Spatiales [Toulouse] (CNES)-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Météo France-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire Midi-Pyrénées (OMP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Centre National de la Recherche Scientifique (CNRS), Laboratoire Ecologie Fonctionnelle et Environnement (LEFE), Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Observatoire Midi-Pyrénées (OMP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université de Toulouse (UT)
- Subjects
Aqueous solution ,010504 meteorology & atmospheric sciences ,Isotopes of copper ,Phototrophic biofilms ,Biofilm ,Geology ,Fractionation ,biochemical phenomena, metabolism, and nutrition ,010502 geochemistry & geophysics ,01 natural sciences ,6. Clean water ,Isotopic signature ,13. Climate action ,Geochemistry and Petrology ,[SDU]Sciences of the Universe [physics] ,Environmental chemistry ,Desorption ,Efflux ,0105 earth and related environmental sciences - Abstract
The metal excretion and metal sorption are two important microbial processes in the regulation of intracellular metal concentration. However, the contribution of freshwater phototrophic biofilm to metal efflux in the environment and its related isotopic fractionation remain poorly known. In this study, Cu efflux from a mature phototrophic biofilm and related Cu isotopic fractionation between the biofilm and aqueous solution were studied over 4 days in closed batch and open drip-flow reactors (BR and DFR, respectively). The impact of a 48-h drying event on Cu efflux from the biofilm and its isotopic signature was quantified in the BR. Cu excretion from the biofilm depended on Cu concentration in the biomass and did not show a latent phase. For the wet biofilm, in DFR, the Cu efflux rate decreased over time whereas in BR, Cu efflux exhibited fluctuations with a net re-sorption phase. During short-term early excretion over the first 4 h (BR) and 24 h (DFR), the enrichment of solution in heavy isotopes with a Δ65Cu(sol–biofilm) of +0.7 ± 0.2‰ could be explained by a combination of i) desorption via competition between H+ and Cu2+ for surface sites and ii) release of isotopically heavy Cu(II)-organic complexes. In addition, there was a retention of isotopically light Cu (I) within the cells which is consistent with the biofilm ability to reduce Cu. With further exposure of the wet biofilm to the solution, a progressive decrease of Δ65Cu(sol–biofilm), down to 0 and −0.36‰ respectively in BR and DFR after 96 h, could be explained by an active efflux of Cu(I) and by a passive diffusion of Cu2+, both of these processes favoring light isotopes. The re-hydrated and wet biofilms showed distinctly different behavior during excretion, in terms of magnitude of the flux and direction of the fractionation for long term exposure. Indeed, the efflux from the re-hydrated biofilm was ten times higher than the one from the wet biofilm and the re-hydrated biofilm did not exhibit a decrease of Δ65Cu(sol–biofilm) after 24 h of reaction. This could be related to partial devitalization of the biofilm during drying, producing a release of isotopically heavy Cu and decreasing the intensity of Cu(I) active efflux of light isotopes. Taken together, the Cu isotopic signature in natural aquatic environments containing phototrophic biofilms varies up to 1‰ on a daily scale.
- Published
- 2019
41. Cu isotope fractionation during reduction processes in aqueous systems: evidences from electrochemical deposition
- Author
-
Marina Lazarov, Stefan Weyer, Harald Behrens, and Dongmei Qi
- Subjects
Aqueous solution ,010504 meteorology & atmospheric sciences ,Isotopes of copper ,Stable isotope ratio ,Analytical chemistry ,chemistry.chemical_element ,Electrolyte ,Atmospheric temperature range ,010502 geochemistry & geophysics ,Electrochemistry ,01 natural sciences ,Copper ,Geophysics ,Isotope fractionation ,chemistry ,Geochemistry and Petrology ,Geology ,0105 earth and related environmental sciences - Abstract
Redox processes are ubiquitous in Earth science, and redox transitions often lead to large fractionations of the stable isotopes of many transition metals such as copper. To get insights into the mechanisms of isotope fractionations induced by electrochemical processes, we examine the behavior of copper isotopes during the reduction reaction Cu2+ + 2e− = Cu0. All experiments have been conducted by applying a controlled current between the working electrode and the auxiliary electrode, i.e., the galvanostatic electrodeposition technique, in aqueous CuSO4 solutions. Controlling parameters were tested by varying electrolyte concentration (0.01–1 mol kg−1), stirring speed (0–500 rpm), current (0.1–0.5 A), time (35–600 s), and temperature (5–80 °C). In all cases, the plated Cu metal is enriched in the light isotope (63Cu) with respect to the solution. At room temperature, the Cu isotopic fractionation between the electroplated Cu and electrolyte is found to increase with electrolyte concentration and stirring speed, and to decrease with current and run duration. These trends can be interpreted by three competing processes: copper transport in the solution, kinetics of electrochemical reduction of copper ions and surface diffusion at the electrode, i.e., transport becomes important at low copper concentration, low stirring speed, high currents and large amount of copper precipitation. Copper isotope fractionation has a maximum near 35 °C, decreasing both towards higher and lower temperatures. In the temperature range of 35–80 °C, the dependence of temperature on isotope fractionation can be described by $$ \Delta^{65} {\text{Cu}}_{{{\text{Cu}}\left( 0 \right) - {\text{Cu}}({\text{II}}){\text{aq}}}} = - \left( {0.27 \pm 0.04} \right) \times 10^{6} T^{ - 2} + \left( {0.16 \pm 0.34} \right), $$ where ∆65CuCu(0)–Cu(II)aq (‰) represents the copper isotopic composition differences between the product (electroplated copper) and the reactant (electrolyte solution, CuSO4(aq)), and T is the temperature in K. At low temperature (down to 5 °C), a noticeable deviation from this trend suggests a change in the controlling mechanism, i.e., transport in the solution becomes important. Our findings are best explained by a two-step reduction process including reduction from Cu(II) to Cu(I) and a subsequent reduction of Cu(I) to Cu(0). The good agreement of our high-temperature data with the results from Ehrlich et al. (2004), who used a different experimental approach to precipitate Cu(I) mineral from CuSO4 solution, implies that transformation of Cu(II) to Cu(I) dominates the isotope fractionation observed during electrochemical reduction of Cu(II) to Cu(0). These findings support that copper isotopes can be used as effective tracers of redox processes. They may have implications to processes in hydrothermal systems and the formation of ore deposits, e.g., volcanic-hosted massive sulfides, as well as to processes in near surface aquatic environment and related supergene processes.
- Published
- 2019
42. Copper isotope ratios in Cis-Urals copper sandstones and products of their processing as a tool for uncovering the Bronze Age smelting activities
- Author
-
D. V. Kiseleva, M. N. Ankushev, M. V. Streletskaya, M. V. Chervyakovskaya, S. V. Bogdanov, S. V. Karpova, E. S. Shagalov, A. M. Yuminov, and V. V. Tkachev
- Subjects
Flux (metallurgy) ,Isotopes of copper ,Chemistry ,Bronze Age ,visual_art ,Metallurgy ,Smelting ,visual_art.visual_art_medium ,chemistry.chemical_element ,Slag ,Malachite ,Ingot ,Copper - Abstract
Copper isotope ratios are determined by MC-ICP-MS in a number of Cis-Urals copper sandstones and products of their processing. Malachite crusts are characterized by positive δ65Cu (+1.33‰÷+1.96‰) whereas the sludge with flux additives and experimental glassy slag have the lowest negative δ65Cu values (-4.87‰÷-4.32‰). δ65Cu = −0.54‰ is found for copper ingot obtained during the experimental smelting. Copper matte and sludge have negative δ65Cu values ranging from -2.33 to -2.61‰.
- Published
- 2019
43. Paired dissolved and particulate phase Cu isotope distributions in the South Atlantic
- Author
-
Derek Vance, Eric P. Achterberg, Christian Schlosser, Angela Milne, Corey Archer, Susan H. Little, Maeve C. Lohan, Leverhulme Trust, and Natural Environment Research Council (NERC)
- Subjects
Geochemistry & Geophysics ,010504 meteorology & atmospheric sciences ,MARINE-SEDIMENTS ,Isotopes of copper ,Geotraces ,ORGANIC-LIGANDS ,PLASMA-MASS SPECTROMETRY ,010502 geochemistry & geophysics ,01 natural sciences ,Deep sea ,South Atlantic ,DEEP-OCEAN ,Geochemistry and Petrology ,TRACE-ELEMENTS ,0402 Geochemistry ,14. Life underwater ,Scavenging ,0105 earth and related environmental sciences ,Particulate ,Science & Technology ,Copper isotopes ,GEOTRACES ,Dissolved ,ARCTIC PACIFIC-OCEAN ,Geology ,ZINC ISOTOPES ,Particulates ,NORTH-ATLANTIC ,ACID CHELATING RESIN ,TASMAN SEA ,0403 Geology ,13. Climate action ,Benthic zone ,Environmental chemistry ,Physical Sciences ,Isotopes of zinc ,Seawater ,0406 Physical Geography And Environmental Geoscience - Abstract
Copper (Cu) is both an essential micronutrient and toxic to photosynthesizing microorganisms at low concentrations. Its dissolved vertical distribution in the oceans is unusual, being neither a nutrient-type nor scavenged-type element. This distribution is attributed to biological uptake in the surface ocean with remineralisation at depth, combined with strong organic complexation by dissolved ligands, scavenging onto particles, and benthic sedimentary input. We present coupled dissolved and particulate phase Cu isotope data along the UK-GEOTRACES South Atlantic section, alongside higher resolution dissolved and particulate phase Cu concentration measurements. Our dissolved phase isotope data contribute to an emerging picture of homogeneous deep ocean δ65Cu, at about +0.65‰ (relative to NIST SRM 976). We identify two pools of Cu in the particulate phase: a refractory, lithogenic pool, at about 0‰, and a labile pool accessed via a weak acidic leach, at about +0.4‰. These two pools are comparable to those previously observed in sediments. We observe deviations towards lighter δ65Cu values in the dissolved phase associated with local enrichments in particulate Cu concentrations along the continental slopes, and in the surface ocean. Copper isotopes are thus a sensitive indicator of localised particle-associated benthic or estuarine Cu inputs. The measurement of Cu isotopes in seawater is analytically challenging, and we call for an intercalibration exercise to better evaluate the potential impacts of UV-irradiation, storage time, and different analytical procedures. ISSN:0009-2541 ISSN:1872-6836
- Published
- 2018
44. Tracing Copper Migration in the Tongling Area through Copper Isotope Values in Soils and Waters
- Author
-
Joaquin Ruiz, Peter D'Amico, Ryan Mathur, Glen Brumm, Linda Godfrey, Jingwen Su, and Shiming Song
- Subjects
China ,Isotopes of copper ,Health, Toxicology and Mutagenesis ,chemistry.chemical_element ,lcsh:Medicine ,Weathering ,010501 environmental sciences ,mining ,010502 geochemistry & geophysics ,01 natural sciences ,Article ,chemistry.chemical_compound ,Soil ,Rivers ,copper concentration ,Soil Pollutants ,copper isotopes ,Groundwater ,0105 earth and related environmental sciences ,Tailings dam ,lcsh:R ,Public Health, Environmental and Occupational Health ,Tongling ,Copper ,Tailings ,Sulfide minerals ,Copper sulfide ,chemistry ,Copper Radioisotopes ,Environmental chemistry ,Soil water ,Environmental science ,Water Pollutants, Chemical ,Environmental Monitoring - Abstract
Copper mining in Tongling has occurred since the Bronze Age, and this area is known as one of the first historic places where copper has been, and is currently, extracted. Multiple studies have demonstrated, through concentrated work on soils and waters, the impact of mining in the area. Here we present copper isotope values of 13 ore samples, three tailing samples, 20 water samples (surface and groundwater), and 94 soil samples (15 different profiles ranging in depth from 0&ndash, 2 m) from proximal to distal (up to 10 km) locations radiating from a tailings dam and tailings pile. Oxidation of the copper sulfide minerals results in isotopically heavier oxidized copper. Thus, copper sourced from sulfide minerals has been used to trace copper in mining and environmental applications. At Tongling, higher copper isotope values (greater than 1 per mil, which are interpreted to be derived from copper sulfide weathering) are found both in waters and the upper portions of soils (5&ndash, 100 cm) within 1 km of the source tailings. At greater than 1 km, the soils do not possess heavier copper isotope values, however, the stream water samples that have low copper concentrations have heavier values up to 6.5 km from the source. The data suggest that copper derived from the mining activities remains relatively proximal in the soils but can be traced in the waters at greater distances.
- Published
- 2018
45. Use of non-traditional heavy stable isotopes in archaeological research
- Author
-
Jay Stephens, Mihai N. Ducea, Joaquin Ruiz, and David Killick
- Subjects
Archeology ,Supergene (geology) ,Provenance ,Isotope fractionation ,chemistry ,Stable isotope ratio ,Hypogene ,Isotopes of copper ,Smelting ,Geochemistry ,chemistry.chemical_element ,Copper ,Geology - Abstract
Recent analytical developments in the field of mass spectrometry have made possible accurate measurements of “non-traditional” isotopic ratios of elements such as Fe, Cu, Ag, Sn, Sb and Hg. The stable isotopes of these elements do not have any radioactive parents, but their ratios undergo limited fractionation from various causes, most of them mass-dependent. These effects can lead to variation in isotopic ratios of natural materials (minerals, rocks, ores, etc.) and in archaeological artifacts derived from them. Research since 2010 has investigated whether variation in these isotopic ratios can be used to infer the geological provenance of archaeological materials, including bronze and glass. Here we review recent research on these isotopic systems in archaeology, their principal applications, as well as expected future developments in their use. We conclude that none of these isotopic systems are likely to be very useful for provenance, mostly because of limited ranges of isotopic ratios and/or extensive overlap between the isotopic ratios of most geological sources. Copper isotope ratios are however a reliable method for inferring the type of ore (supergene versus hypogene) smelted to produce copper, and recent studies indicate that silver isotope ratios can also be applied to this effect.
- Published
- 2021
46. Investigation of α-induced Reaction on Copper Isotopes for Energy Range of 15-50 Mev
- Author
-
Baye Zinabe Kebede
- Subjects
Range (particle radiation) ,Work (thermodynamics) ,Reaction mechanism ,Materials science ,Isotope ,Projectile ,Isotopes of copper ,020209 energy ,Analytical chemistry ,02 engineering and technology ,030218 nuclear medicine & medical imaging ,03 medical and health sciences ,Cross section (physics) ,0302 clinical medicine ,0202 electrical engineering, electronic engineering, information engineering ,Particle ,Nuclear Experiment - Abstract
The present work was done on alpha induced reaction mechanics on two natural coppers isotopes for the energy range of 15 to 30 Mev were investigated. The reaction channels for the total cross section 63Cu (α, n) 66Ga, 65Cu (α, 2n)67Ga, 63Cu(α, pn) 65Cu and 65Cu(α, n)68Ga were studied. The experimental data of reaction cross section COMPLETE code have been used. The aim study was compared experimental and theoretical reaction cross section both compound and pre-compound reaction and know the property, the reaction mechanism of the projectile particle reacts with target nuclei. The theoretical result was obtained from international atomic energy agency, exchange format data source. We understood the reaction mechanisms and the property of fragment particles during the reaction. Level density parameter and exaction number were varied to become good agreement between the calculated and measured data. In this study different dependency reaction cross section, the projectile energy was observed between the production of 67Ga and 65Zn. In alpha induced reaction with copper isotopes 66Ga, 67Ga, 68Ga and 65Zn are produced. Normally the calculation using a COMPLET code provides good outcome for the reaction cross-section of alpha induced reaction on low projectile energy. During the study of the reaction compound and pre-equilibrium reaction are occurred but direct reaction was almost not expected. Direct reaction is required to very large amount of energy.
- Published
- 2021
47. Development of Two New Copper Isotope Standard Solutions and their Copper Isotopic Compositions
- Author
-
Zhian Bao, Wengting Yuan, Honglin Yuan, Fang Huang, Kaiyun Chen, and Sheng-Ao Liu
- Subjects
Chemistry ,Stable isotope ratio ,Isotopes of copper ,010401 analytical chemistry ,Radiochemistry ,Copper wire ,chemistry.chemical_element ,Geology ,Standard solution ,010502 geochemistry & geophysics ,Mass spectrometry ,01 natural sciences ,Copper ,Isotopic composition ,0104 chemical sciences ,Isotopic signature ,Geochemistry and Petrology ,0105 earth and related environmental sciences - Abstract
In this study, two new laboratory reference solutions for testing Cu isotopic composition were established and investigated. Two commercially available pure copper products, copper plate and copper wire, were dissolved in 1000-ml Teflon® bottles, to produce 200 μg ml−1 stock solutions (hereafter referred to as NWU-Cu-A and NWU-Cu-B), and cryogenically stored. The Cu isotopic compositions of the two samples were determined in three different laboratories using multi-collector inductively coupled plasma-mass spectrometry, and the Cu isotopic compositions obtained from the standard-sample bracketing method were consistent within the two standard deviation (2s) range. The Cu isotopic compositions of the NWU-Cu-A and NWU-Cu-B standard solutions were δ65Cu = +0.91 ± 0.03‰ (2s, n = 42) and δ65Cu = −0.05 ±0.03‰ (2s, n = 49), respectively, relative to the reference material NIST SRM 976.
- Published
- 2016
48. Neutron-Induced Medical Radioisotope Production in a Conceptual Accelerator-Driven System, Fueled with Uranium Carbide
- Author
-
Saltuk Selcuklu, Ahsen Arslan, Gizem Bakir, Gamze Genç, Hüseyin Yapıcı, and [Arslan, A. B. -- Selcuklu, S. B. -- Genc, G. -- Yapici, H.] Erciyes Univ, Enerji Sistemleri Muhendisligi Bolumu, Kayseri, Turkey -- [Bakir, G.] Cumhuriyet Univ, Enerji Sistemleri Muhendisligi Anabilimdali, Sivas, Turkey
- Subjects
Materials science ,Fissile material ,Isotope ,Isotopes of copper ,Fission ,020209 energy ,Nuclear engineering ,General Physics and Astronomy ,chemistry.chemical_element ,02 engineering and technology ,030218 nuclear medicine & medical imaging ,Coolant ,Nuclear physics ,03 medical and health sciences ,chemistry.chemical_compound ,0302 clinical medicine ,chemistry ,0202 electrical engineering, electronic engineering, information engineering ,Neutron ,Uranium carbide ,Nuclear Experiment ,Carbon - Abstract
2nd International Conference on Computational and Experimental Science and Engineering (ICCESEN) -- OCT 14-19, 2015 -- Kemer, TURKEY, WOS: 000384810700018, In this study, the medical radioisotope production performance of a conceptual accelerator-driven system is investigated. Lead-bismuth eutectic is used as target material. The fuel core of the considered accelerator-driven system is divided into ten subzones, loaded with uranium carbide and various isotopes (isotopes of copper, gold, cobalt, holmium, rhenium, scandium, and thulium) and cooled with light water. As is known, light water is an effective moderator of neutrons as well as a good coolant. The fuel and the isotopes are separately placed as cylindrical rods with a cladding of carbon composite. The volume fractions of fuel, isotope, cladding and coolant are selected as 25%, 35%, 10% and 30%, respectively. The copper rods are placed into the first five subzones due to the fact that copper isotopes have low capture cross-section. In the case of the each radioisotope production, one of the other considered isotopes that have higher capture cross-section are placed into the following five subzones for optimization of fission, fissile breeding and radioisotope production. The graphite zone is located around the fuel core to reflect the escaping neutrons. Boron carbide (B4C) is used as shielding material. In order to produce more neutrons (about 25-30 neutrons per 1 GeV proton), the target is irradiated with a continuous beam of 1 GeV protons. All neutronic computations have been performed with the high-energy Monte Carlo N-Particle Transport Code using the LA150 data library. The neutronic results obtained from these calculations show that the examined accelerator-driven system has a high neutronic capability, in terms of production of thermal power, fissile fuels, and medical radioisotopes.
- Published
- 2016
49. Tracing the Source of Native Copper Mineral Specimens with Copper Isotope Values
- Author
-
Marc Wilson, Ryan Mathur, and Debra L. Wilson
- Subjects
010506 paleontology ,Native copper ,Mineral ,Isotopes of copper ,Chemistry ,Stratigraphy ,Mineralogy ,Economic Geology ,Geology ,Tracing ,010502 geochemistry & geophysics ,01 natural sciences ,0105 earth and related environmental sciences - Abstract
A common problem in many collections is one of mislabeled or unlabeled specimens. The practice of correcting errors and restoring lost species and locality and historical data is known as the reass...
- Published
- 2016
50. Cu diffusion in a basaltic melt
- Author
-
Youxue Zhang and Peng Ni
- Subjects
chemistry.chemical_classification ,010504 meteorology & atmospheric sciences ,Sulfide ,Isotopes of copper ,Diffusion ,Analytical chemistry ,Mineralogy ,chemistry.chemical_element ,Activation energy ,010502 geochemistry & geophysics ,Thermal diffusivity ,01 natural sciences ,Copper ,Silicate ,chemistry.chemical_compound ,Geophysics ,chemistry ,Geochemistry and Petrology ,Kinetic fractionation ,0105 earth and related environmental sciences - Abstract
Recent studies suggest a potential role of diffusive transport of metals (e.g., Cu, Au, PGE) in the formation of magmatic sulfide deposits and porphyry-type deposits. However, diffusivities of these metals are poorly determined in natural silicate melts. In this study, diffusivities of copper in an anhydrous basaltic melt ( 2 O) were measured at temperatures from 1298 to 1581 °C, and pressures of 0.5, 1, and 1.5 GPa. Copper diffusivities in anhydrous basaltic melt at 1 GPa can be described as: D Cu basalt = exp [ − ( 14 . 12 ± 0 . 50 ) − 11813 ± 838 T ] where D Cu basalt is the diffusivity in m 2 /s, T is the temperature in K, and errors are given at 1σ level. A fitting of all experimental data considering the pressure effect is: D Cu basalt = exp [ − ( 13 . 59 ± 0 . 81 ) − ( 12153 ± 1229 ) + ( 620 ± 241 ) P T ] where P is the pressure in GPa, which corresponds to a pre-exponential factor D 0 = (1.25 ×÷ 2.2)×10 −6 m 2 /s, an activation energy E a = 101 ± 10 kJ/mol at P = 0, and an activation volume V a = (5.2 ± 2.0)×10 −6 m 3 /mol. The diffusivity of copper in basaltic melt is high compared to most other cations, similar to that of Na. The high copper diffusivity is consistent with the occurrence of copper mostly as Cu + in silicate melts at or below NNO. Compared to the volatile species, copper diffusivity is generally smaller than water diffusivity, but about one order of magnitude higher than sulfur and chlorine diffusivities. Hence, Cu partitioning between a growing sulfide liquid drop and the surrounding silicate melt is roughly in equilibrium, whereas that between a growing fluid bubble and the surrounding melt can be out of equilibrium if the fluid is nearly pure H 2 O fluid. Our results are the first copper diffusion data in natural silicate melts, and can be applied to discuss natural processes such as copper transport and kinetic partitioning behavior in ore formation, as well as copper isotope fractionation caused by evaporation during tektite formation.
- Published
- 2016
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