Copper Isotopic Composition Research Articles

Copper and zinc isotope compositions of pristine eucrites as analogues for differentiated planetary feedstocks

Preferential enrichment of the heavier isotopes of moderately volatile elements (MVE) in samples from asteroids and the Moon have been attributed to volatile loss during the formation and differentiation of their parent bodies. Analogs for planetary feedstocks include the howardite-eucrite-diogenite meteorites, which originate from a differentiated planetesimal or planetesimals, likely including (4) Vesta. Complications arise in the interpretation of volatile depletion in these meteorites, however, due to post-crystallization processes including metamorphism and later impacts that acted upon them. We present new coupled Cu and Zn isotope data for a suite of eucrites that, when combined with published data, show significant ranges (δ65Cu = -1.6 to +0.9‰; δ66Zn = -7.8 to +13.5‰). Exclusion of eucrites that have been affected by metamorphism, impact contamination or surface condensation of isotopically light Zn and Cu leads to a range of ‘pristine’ compositions (δ66Zn = +1.1 ± 2.3‰; δ65Cu = +0.5 ± 0.5‰; 2 St. Dev.), implying inherent MVE variability within the eucrite parent body. As low-mass differentiated bodies, Vesta and the Moon represent endmembers in planet evolution. For the Moon, extensive volatile loss can be explained by a cataclysmic giant impact origin and later magma ocean crystallization. In contrast the parent body of eucrite meteorites likely heterogeneously lost volatile elements and compounds during differentiation. Vesta as the potential source of eucrite meteorites offers an important endmember composition for likely feedstocks to planets, representing the remaining vestige of what was likely to have been a larger population of differentiated objects in the inner Solar System shortly after nebula accretion. Mixing contributions of non-carbonaceous and carbonaceous chondrites constrained by nucleosynthetic Zn isotope anomalies suggests a significant fraction of Earth's accretion could have come from volatile-poor and differentiated planetary feedstocks that would have had limited effects on the bulk silicate Earth (BSE) Zn isotope composition. Furthermore, volatile-poor feedstocks cannot explain the BSE Cu isotope composition, which instead may have been modified by terrestrial core formation. Pristine eucrites offer key insights into early planetesimal differentiation and the role of volatile loss on small mass bodies within nascent solar systems.

Copper and zinc isotopic compositions of methane-derived carbonates: Implications for paleo-methane seepage and paleoenvironmental proxies

Copper and zinc isotopic compositions of methane-derived carbonates: Implications for paleo-methane seepage and paleoenvironmental proxies

Sources of Ore Material in the Platinum-Group Element Deposits of Polar Siberia and the Middle Urals Based on the Data from Radiogenic (Re–Os, Pt–Os) and Stable (Cu, S) Isotopes

Abstract —Understanding the main events of platinum-group element (PGE) ore formation is impossible without analysis of the sources and behavior of major ore-forming components, namely, platinum, osmium, sulfur, and copper, which are important indicators of magmatic and hydrothermal processes. In contrast to the Re–Os isotope system, the radiogenic Pt–Os isotope system, as well as stable isotopes of Cu and S in PGE deposits, are still relatively understudied. Our comprehensive research is aimed at filling this gap. The paper presents data for the Guli massif of ultramafic and alkaline rocks and carbonatites in Polar Siberia and on the zonal Nizhny Tagil and Svetly Bor clinopyroxenite–dunite massifs in the Middle Urals, which include: (1) the contents of the highly siderophile elements (HSE) in whole rocks and platinum-group minerals (PGM), (2) the Re–Os and Pt–Os isotope systematics of chromitite, Os–Ir alloys, and Ru–Os sulfides, (3) the sulfur isotope composition in Ru–Os and Ir–Rh sulfides in primary and secondary PGM assemblages, and (4) the copper isotope composition in Pt–Fe minerals from chromitites and placers. The research was performed using scanning electron microscopy, electron probe microanalysis, and high-precision isotope-geochemical analysis. The high-precision Re–Os and Pt–Os isotope data show that the HSE contents in chromitites and PGM of the Guli massif were controlled by the composition of the mantle source that evolved with near-chondritic time-integrated Re/Os and Pt/Os ratios, which are also typical of the sources of most komatiites and abyssal peridotites. The δ65Cu values of the studied samples of ferroan platinum and isoferroplatinum are identical within the analytical uncertainty and are close to 0‰, which is typical of high-temperature Cu-containing minerals. The sulfur isotope compositions of the Ir–Rh sulfides of the kashinite–bowieite series and of the Ru–Os sulfides of the laurite–erlichmanite series in the primary PGM assemblages indicate that the source of sulfur has a chondritic isotope composition, which is in agreement with the osmium isotope composition of the Ru–Os sulfides and Os–Ir alloys. The heavy sulfur isotope composition (δ34S = 5.6 ± 1.5‰) of As-containing erlichmanite is consistent with its secondary origin. The new data on the isotope compositions of osmium, copper, and sulfur can be used as new important parameters that characterize the sources of PGE mineralization.

Impact of aging on copper isotopic composition in the murine brain.

Aging is the main risk factor for Alzheimer's disease (AD). AD is linked to alterations in metal homeostasis and changes in stable metal isotopic composition can occur, possibly allowing the latter to serve as relevant biomarkers for potential AD diagnosis. Copper stable isotopes are used to investigate changes in Cu homeostasis associated with various diseases. Prior work has shown that in AD mouse models, the accumulation of 63Cu in the brain is associated with the disease's progression. However, our understanding of how the normal aging process influences the brain's isotopic composition of copper remains limited. In order to determine the utility and predictive power of Cu isotopes in AD diagnostics, we aim-in this study-to develop a baseline trajectory of Cu isotopic composition in the normally aging mouse brain. We determined the copper concentration and isotopic composition in brains of 30 healthy mice (WT) ranging in age from 6 to 12 mo, and further incorporate prior data obtained for 3-mo-old healthy mice; this range approximately equates to 20-50yr in human equivalency. A significant 65Cu enrichment has been observed in the 12-mo-old mice compared to the youngest group, concomitant with an increase in Cu concentration with age. Meanwhile, literature data for brains of AD mice display an enrichment in 63Cu isotope compared to WT. It is acutely important that this baseline enrichment in 65Cu is fully constrained and normalized against if any coherent diagnostic observations regarding 63Cu enrichment as a biomarker for AD are to be developed.

Contrasting Cu isotopes in mid-ocean ridge basalts and lower oceanic crust: Insights into the oceanic crustal magma plumbing systems

Magma plumbing systems exert strong controls on the formation and evolution of the oceanic crust during crust accretion. However, plumbing system dynamics based largely on mid-ocean ridge basalts (MORBs) are extremely difficult to constrain because the MORBs are aggregated melts and original information may have been blurred. Copper isotopic compositions of lower crustal gabbroic cumulates effectively archive early-stage histories because sulfides constitute the dominant Cu budget of gabbroic cumulates and are largely isolated from subsequent magma filtering processes. Here, we present Cu isotopes of a suite of gabbroic cumulates from the ultraslow-spreading Southwest Indian Ridge (Hole U1473A), and MORBs from the South Mid-Atlantic Ridge and East Pacific Rise. The δ65Cu of the MORBs from this study (+0.04 ‰ to +0.19 ‰) match those of previous MORB analyses, indicating uniform δ65Cu at various spreading rates. In contrast, the δ65Cu of gabbroic rocks vary significantly (−1.14 ‰ to 0.87 ‰), exceeding by far the range known for peridotites. The Cu budget of these gabbroic rocks is hosted in sulfides and the mantle-like S isotopic compositions of sulfides indicate their origin of igneous processes. These results thus suggest that magma accumulation and sulfide segregation would lead to notable Cu isotopic fractionation in the lower oceanic crust. We propose that repeated recharging of primitive melts and efficient mixing of melts within the plumbing system can buffer the removal of early 63Cu-rich sulfides from sulfide-saturated MORBs. The discrepancy in δ65Cu between lower oceanic crust and MORBs is a natural consequence of continuous replenishment that occurs concurrently with melt-rock interaction, mixing, crystallization and extraction, irrespective of the oceanic settings. The consistent δ65Cu in MORBs (0.09 ± 0.08 ‰) and komatiites (0.06 ± 0.06 ‰) further indicates that their Cu isotopes reflect the mean mantle source composition, providing a robust δ65Cu for bulk silicate Earth (BSE) of 0.08 ± 0.08 ‰ (2sd). Accordingly, we propose that in open sub-ridge plumbing systems, other incompatible element isotopes and ratios of elements with similar incompatibility in MORBs as Cu isotopes suggest, could also represent mean mantle source compositions.

Copper Isotope Compositions Measured Using a Sapphire Dual Path MC-ICPMS with a Collision/Reaction Cell.

We present a new approach to Cu isotopic measurements using a state-of-the-art Nu Sapphire multicollector inductively coupled plasma source mass spectrometer equipped with a collision/reaction cell (CRC-MC-ICPMS). We investigate the effects of Na doping and Cu concentration mismatch between bracketing standard and unknown samples and demonstrate the efficacy of introducing a He-H2 gas mix into the CRC to efficiently eliminate the sample matrix-based 40Ar23Na+ isobaric interference on 63Cu+. This capability is crucial when measuring samples with high Na/Cu ratios, such as some biological samples, which have significantly different chemical compositions compared to most geological samples. Moreover, considering the necessity of obtaining large data sets for biological samples to ensure reliable interpretations, the implementation of a CRC for mitigating the 40Ar23Na+ interference offers the advantage of minimizing the requirement for extensive Cu chemical separation procedure prior to Cu isotopic measurements. Our results demonstrate that the accurate determination of the δ65Cu values is achievable for samples with Na/Cu concentration ratios of up to ∼65, even when measuring 100 ppb Cu solutions (equivalent to a signal of ∼3.5-4 V total Cu). Furthermore, our results showcase a good short-term repeatability on δ65Cu for pure Cu standard solutions (NIST SRM 976 and Cu-IPGP), typically of 0.05‰ (2 SD) when measuring >50 ppb Cu solutions. Our long-term external reproducibility stands at approximately 0.07‰ (2 SD). This value accounts for the variable Cu concentrations analyzed across the different analytical sequences (from 10 to 100 ppb Cu solutions). To validate the robustness of our analytical method, we first conduct a comparison between data sets from mice brains processed twice through column chemistry using a Thermo Finnigan Neptune MC-ICPMS and a Nu Sapphire CRC-MC-ICPMS in CRC mode. This comparison serves to verify the reliability of our method for measuring Cu isotopic composition using the CRC on samples with a low Na/Cu ratio after traditional chemical processing. Then, we compare the data sets obtained for biological standards (tuna fish ERM-CE 464 (IRMM) and human serum Seronorm Trace Elements Serum L-1) processed either once, or twice, through column chemistry and demonstrate that the CRC allows accurate Cu isotopic measurements of the samples processed only once and therefore with a higher Na/Cu ratio.

Cu isotope patterns of whole rocks in the Kerman porphyry copper belt, southeastern Urumieh Dokhtar magmatic arc, Iran

This study presents copper isotope compositions of mineralized whole-rock samples from the Kerman porphyry copper belt (KPCB) southeast of the Urumieh Dokhtar magmatic arc. Samples for this study were specifically collected from the Sar Cheshmeh, Meiduk, Iju, SarKuh, Darreh Zar, Bagh Khoshk, and Jebal Barez deposits and investigated to study the application of Cu isotopes to mineral exploration. While in the leached cap zone of the deposits, δ65Cu values range between −3.41 to 5.82 ‰ (avg. 0.42 ‰), in the supergene enriched zone of these deposits the relatively higher δ65Cu content ranges from 5.18 to 8.71 ‰ (avg. 7.17 ‰), and in the hypogene zone, the intermediate δ65Cu values range from 1.49 to 7.31 ‰ (avg: 4.36 ‰). Most measured δ65Cu values in these investigated porphyry copper deposit are positive, which indicates the presence of a Cu − enriched zone. In the enriched leached cap zones, the δ65Cu of the Darreh Zar and Sar Cheshmeh deposits are overall higher relative to the Iju, Meiduk, SarKuh, and Bagh Khoshk deposits, and these higher δ65Cu values are associated with the highest Cu grade and tonnage in the Sar Cheshmeh and Darreh Zar deposits. It is therefore plausible to conclude that the higher δ65Cu value in the leached areas are diagnostic of the high concentration of copper.These findings are complemented by the presence of Cu(II) carbonates, silicates, and Fe − oxides in each sample that has resulted in the enrichment of 65Cu, relative to the remnant sulfides with a wider copper isotope range. In addition, there is a general shift toward higher δ65Cu isotope values relative to the inferred precursor minerals. The overall apparent weathering and oxidative dissolution is likely to have generated isotopically heavier fluids and lighter residual minerals. The elevated δ65Cu of the bulk samples from porphyry Cu deposits in KPCB is consistent with a preferential loss of 63Cu into fluids during the segregation of aqueous fluid–melt. This is best explained by several pulses of hypogene magmatic fluid which led to repeated enrichment in 65Cu in the magmatic system. It is plausible to conclude that copper isotope values in these mineralized samples can be used as an effective exploration tool to identify buried porphyry Cu systems.

Copper isotope ratios in serum do not track cancerous tumor evolution, but organ failure.

Relative to healthy controls, lighter copper isotopic compositions have been observed in the serum of breast cancer and end-stage liver disease patients, raising the possibility that Cu isotope ratios could be used as a tracer for disease progression. Here, we assess the potential of natural Cu isotopic variations (expressed as δ65Cu) as diagnostic tools for cancer progression and/or liver failure by performing a first-order analysis of Cu isotopic cycling in the human body. Using a box model, we simulate the kinetics of Cu mass transfer throughout significant reservoirs in the body, allowing isotopic fractionation to occur during Cu uptake/release from these reservoirs. With this model, we determine under which conditions the serum δ65Cu values would reflect perturbation related to cancer growth and/or liver failure at a level resolvable with modern mass spectrometry. We find that tumor growth alone is unable to explain the light isotopic signature observed in serum. Instead, we find that metabolic changes to the liver function resulting in a ∼1‰ isotope fractionation during Cu uptake from the blood into the liver can readily explain the long-term serum isotopic shift of ∼0.2‰ observed in cancer patients. A similar fractionation (∼1.3‰) during Cu uptake into the liver also readily explains the -1.2‰ shift observed in the serum of cirrhosis patients with ascites, suggesting a potentially common driver of isotopic fractionation in both cases. Using this model, we then test hypotheses put forward by previous studies and begin to probe the mechanisms behind the measured isotopic compositions.

Contrasting copper concentrations and isotopic compositions in two Great Lakes watersheds

Copper (Cu) stable isotopes can elucidate the biogeochemical controls and sources governing Cu dynamics in aquatic environments, but their application in larger rivers and catchments remains comparatively scarce. Here, we use major and trace element hydrogeochemical data, Cu isotope analyses, and mixing modeling, to assess Cu loads and sources in two major river systems in Ontario, Canada. In both the Spanish River and Trent River catchments, aqueous hydrochemical compositions appeared reasonably consistent, but Cu concentrations were more variable spatially. In the Spanish River, waters near (historic) industrial mining activities displayed positive Cu isotope compositions (δ65CuSRM-976 between +0.75 ‰ and +1.01 ‰), but these signatures were gradually attenuated downstream by mixing with natural background waters (δ65Cu −0.65 ‰ to −0.16 ‰). In contrast, Trent River waters exhibited more irregular in-stream Cu isotope patterns (δ65Cu from −0.75 ‰ to +0.21 ‰), beyond the variability in Cu isotope signatures observed for adjacent agricultural soils (δ65Cu between −0.26 ‰ and +0.30 ‰) and lacking spatial correlation, reflective of the more diffuse sourcing and entwined endmember contributions to Cu loads in this catchment. This work shows that metal stable isotopes may improve our understanding of the sources and baseline dynamics of metals, even in large river systems.

Copper Isotope Composition of Pt–Fe Minerals from the Nizhny Tagil Massif, Middle Urals: First Results

In order to provide further insights into the origin of Pt–Fe minerals, this study presents the first copper isotope data for Pt–Fe minerals from the Nizhny Tagil massif, an international standard of the zoned Ural-type complexes. The chemical and isotopic composition of Pt–Fe minerals were determined by electron microprobe analysis, chemical sample preparation with selective chromatographic separation of copper from a solution of the studied sample, followed by high-precision determination of the δ65Cu value using multiple-collector inductively coupled plasma mass-spectrometry. The majority of platinum group minerals (PGM) from chromitites of the Alexandrovsk Log and Krutoy Log deposits within the Nizhny Tagil massif are formed by Pt–Fe minerals, among which high-temperature ferroan platinum (Pt2Fe) containing subordinate inclusions of Os–Ir alloys and laurite (RuS2) predominate over other PGM. The concentrations of copper and δ65Cu values in the studied samples of ferroan platinum vary from 0.4 to 1.4 wt % Cu and from –0.37 to 0.26‰, respectively. Secondary low-temperature PGM assemblage is represented by the tetraferroplatinum (PtFe)—tulameenite (PtFe0.5Cu0.5) solid solutions series. The concentrations of copper in these PGM vary in the range of 6.8–11.3 wt %; the values of δ65Cu are characterized by lighter Cu-isotopic compositions ranging from –1.15 to –0.72‰. The lighter Cu-isotopic composition in secondary Cu-bearing PGM compared to that in ferroan platinum (δ65Cu = –1.01 ± 0.17‰, n = 8 and δ65Cu = 0.03 ± 0.23‰, n = 7, respectively) is consistent with a secondary nature of isotopic variations, due to evolved composition of the ore-forming fluid during the low-temperature formation of the tetraferroplatinum—tulameenite solid solution series.

Metallomic profiling and natural copper isotopic signatures of childhood autism in serum and red blood cells

Excessive exposure to metals directly threatens human health, including neurodeve lopment. Autism spectrum disorder (ASD) is a neurodevelopmental disorder, leaving great harms to children themselves, their families, and even society. In view of this, it is critical to develop reliable biomarkers for ASD in early childhood. Here we used inductively coupled plasma mass spectrometry (ICP-MS) to identify the abnormalities in ASD-associated metal elements in children blood. Multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) was applied to detect isotopic differences in copper (Cu) for further assessment on account of its core role in the brain. We also developed a machine learning classification method for unknown samples based on a support vector machine (SVM) algorithm. The results indicated significant differences in the blood metallome (chromium (Cr), manganese (Mn), cobalt (Co), magnesium (Mg), and arsenic (As)) between cases and controls, and a significantly lower Zn/Cu ratio was observed in the ASD cases. Interestingly, we found a strong association of serum copper isotopic composition (δ65Cu) with autistic serum. SVM was successfully applied to discriminate cases and controls based on the two-dimensional Cu signatures (Cu concentration and δ65Cu) with a high accuracy (94.4%). Overall, our findings revealed a new biomarker for potential early diagnosis and screening of ASD, and the significant alterations in the blood metallome also helped to understand the potential pathogenesis of ASD in terms of metallomics.

The use of copper isotopes for understanding metal transfer mechanisms within the continuum mine-river-dam (Huelva Region, Spain).

Mining areas and in particular those containing massive sulfides have left a heavy environmental legacy with soils and hydrographic networks highly contaminated with metals and metalloids as for example in the Iberian Pyrite Belt (Huelva, Spain). Here, we present new data on copper (Cu) isotopic composition of waters and solids collected along a continuum Mine (Tharsis)-River (Meca)-Lake (Sancho) in the Iberian Pyrite Belt. Our results show that the isotopic signature of pit lakes is spatially variable, but remains stable over the seasons; this signature seems to be controlled by water-rock interaction processes. The data obtained on the Meca River imply a number of attenuation processes such as decrease in the metal concentration by precipitation of secondary minerals. This is accompanied by preferential retention of the heavy isotope (65Cu) with a possibility of living organisms (e.g., algae) participation. The terminal Sancho lake demonstrated constant isotopic signature over the entire depth of the water column despite sizable variations in Cu concentrations, which can be tentatively explained by a superposition of counter-interacting biotic and abiotic processes of Cu fractionation. Overall, the understanding of the isotopic variations along the hydrological continuum is useful for a better understanding of metal element transfer within mining environments and surrounding surface waters.

Isotopic composition of serum zinc and copper in healthy children and children with autism spectrum disorder in North America.

To better understand zinc and copper regulation and their involvement in various biochemical pathways as it relates to autism spectrum disorder (ASD), isotopic composition of serum zinc and copper were evaluated in both healthy children and children with ASD in North America. No significant difference in isotopic composition of serum zinc or copper with respect to healthy controls and ASD children were identified. However, the isotopic composition of serum copper in boys was found to be enriched in 65Cu in comparison to previously published healthy adult copper isotopic composition. Furthermore, in both boys and girls, the average isotopic composition of serum zinc is heavier than previously published healthy adult isotopic zinc composition. There was also a negative association between total zinc concentrations in serum and the zinc isotopic composition of serum in boys. Finally, children with heavier isotopic composition of copper also showed a high degree of variability in their zinc isotopic composition. While numerous studies have measured the isotopic composition of serum zinc and copper in adults, this is one of the first studies which measured the isotopic composition of serum copper and zinc in children, specifically those diagnosed with ASD. The results of this study showed that age and gender specific normal ranges of isotopic composition must be established to effectively use isotopic composition analysis in studying various diseases including ASD.

Can copper isotope composition in oysters improve marine biomonitoring and seafood traceability?

This study provides the first geographic and temporal large-scale analysis of Cu stable isotope compositions in indigenous oysters to biomonitor anthropogenic Cu inputs in aquatic systems. It includes oyster samples from French marine environments with distinct Cu-pollution levels and histories and extends over several decades of biomonitoring. Sample series composed of oysters from the same season and similar size/age intended to avoid biological biases. Oysters in macrotidal estuaries (Loire and Gironde, Western France) display fluctuating Cu concentrations without clear temporal trends, challenging to infer anthropogenic influence. Conversely, the time series of their Cu isotope ratios indicate a constant proportion of natural and anthropogenic Cu sources since the 1980s. In contrast, Cu isotope compositions in oysters from the progressively developing locales (urbanization and recreational boating) of Arcachon and Vilaine bays shift positively over time, along with increasing Cu concentrations. This finding suggests a gradual augmentation in the bioaccumulation of anthropogenic Cu over time. Thus, Cu isotope compositions in oysters is an unambiguous and robust approach to pinpoint anthropogenic Cu contamination in marine biomonitoring. Furthermore, Cu concentrations combined with isotope compositions yield site-specific fingerprints allowing geographic discrimination among oysters. This two-dimensional Cu signature is promising as a tool for seafood traceability.

Iron, copper and zinc isotope compositions of biological reference materials determined by MC-ICP-MS

The one-column method to purify Cu–Fe–Zn for biological isotope analysis provides comprehensive isotope information for biological individuals.

Genesis of the giant Zijinshan epithermal Cu-Au deposit, Fujian Province, southeastern China: Cu-He-Ar isotope perspective

The giant Zijinshan high-sulfidation epithermal Cu-Au deposit is located in the Zijinshan ore field of southeastern China. A sharp boundary separates the upper Au orebodies from lower Cu orebodies at roughly 650 m below the original pit surface, below which digenite is the predominant Cu-bearing mineral. The current discussion revolves over whether the shallow Au and deep Cu mineralization are cogenetic or reflect independent ore-forming episodes, as well as whether the digenite formation is hydrothermal or supergene. In this contribution, we investigate the He-Ar isotope compositions of ore-related sulfides to decipher the source and history of ore-bearing fluids, and use the systematic variation of Cu isotope in Cu-bearing minerals to reveal the hydrothermal (hypogene and supergene) process.A gradual decrease in fluid 3He/4He and 40Ar/36Ar ratios, as well as a sharp drop in 3He/36Ar ratio, reflects the progressive dilution of a magmatic-sourced hydrothermal fluid by meteoric water. Some pyrites have 3He/4He ratios nearly identical to those of mantle fluid, indicating that the ore-forming fluids were mantle-derived with insignificant crust assimilation. The 3He/heat ratios that are higher than those of mid-oceanic ridges, indicating that the heat was transported by convection of low-temperature fluids with hydrothermal fluids rather than direct magma volatile injection. The copper isotope composition of the sulfides (δ65Cu = -3.59 to 1.33 ‰) increases with depth, which was likely caused by the release and downward transport of heavier copper isotopes near the surface. More than half (14 of 24) of these sulfides have a hypogene origin (δ65Cu = -0.05 ± 0.18 ‰), with 9 of 24 samples are likely of supergene origin. Combining with previous study, we confirm that enriched 65Cu reservoir is absent at Zijinshan.Based on the mass-balance of Cu isotopes and the spatial orebody relationship, we conclude that the leaching by meteoric water contributed to the conversion of low-grade initial hypogene Au mineralization into supergene, friable high-grade ore, resulting in the vertical zoning of Au and Cu at Zijinshan. Furthermore, the 65Cu-rich fluids produced by leaching may have lost to the groundwater, resulting in little exploration potential for 65Cu enrichment zone, while the uniform pattern of Cu isotope in the deep indicates a high exploration potential for hypogene Cu mineralization zone at depth.

Shiny bronze in glassy matter: an inconspicuous piece of slag from the Bronze Age mining site of Mušiston (Tajikistan) and its significance for the development of tin metallurgy in Central Asia

This paper aims at contributing to a better understanding of the beginnings of tin and bronze metallurgy in Central Asia by investigating a hitherto unique piece of a bronze slag. The object was originally discovered as a stray find only 4 km away from the large copper-tin deposit of Mušiston in Tajikistan. It contains many prills of bronze and copper as well as small charcoal particles. Radiocarbon dating of the charcoal places the slag in a period between 1900 and 1400 BCE and thus in the Late Bronze Age of the region. This date coincides with radiocarbon dates of relics from underground galleries of the Mušiston deposit. Chemical and microscopic examination demonstrated the slag to be a relic of a co-smelting process, in which a natural assemblage of tin and copper minerals was smelted simultaneously. Both the chemical and the tin and copper isotope compositions clearly link the slag to the nearby polymetallic ores from Mušiston, of which an extensive dataset is presented. The artefact’s lead isotope ratios and increased iron concentration in turn indicate intentional fluxing of the original ore charge with iron-dominated ores. These results are the first tangible evidence of a smelting process of tin ores in the entire region and therefore add a new dimension to the findings from previous mining archaeological investigations. At the same time, the results give significant information about the smelting process of secondary polymetallic ores from Mušiston and help in assessing the scientific data of Bronze Age bronze artefacts from Central Asia.

Light Zn and Cu isotope compositions recorded in ferromanganese crusts during the Cenozoic as evidence for hydrothermal inputs in South Pacific deep seawater

This study presents a high-resolution record of Cu and Zn isotopes in four Fe-Mn crusts from the North and South Pacific oceans. North Pacific crusts were collected on the Apuupuu seamount south of the Hawaiian archipelago and South Pacific crusts were recovered near Rurutu Island in the Tahiti archipelago. Major and trace element compositions suggest that Cu and Zn in these crusts is of hydrogenous origin, i.e., precipitated from seawater, and they may therefore mirror deep seawater metal isotope. We show that Cu and Zn display different isotopic patterns between the North and the South Pacific Oceans but show similar temporal evolution within each geographical area. Copper and Zn isotope composition of both North Pacific crusts vary between 0.57 ‰ to 0.73 ‰ for δ65/63CuNIST976 and 0.97 ‰ to 1.25 ‰ for δ66/64ZnJMC-Lyon. In contrast, South Pacific crusts show resolvable temporal variations, with Cu and Zn isotopic ratios increasing sharply over the last ∼ 6 Ma from 0.16 ‰ to 0.51 ‰ and 0.67 ‰ to 1.09 ‰ respectively. Notably, we observed a positive correlation between δ65/63CuNIST976 and δ66/64ZnJMC-Lyon values in Fe-Mn crusts from the South Pacific. The correlation suggests mixing between two components in Fe-Mn crusts, a hydrothermal component with δ65/63CuNIST976 ∼ 0.2 ‰ and δ66/64ZnJMC-Lyon ∼ 0.7 ‰, and a Pacific deep seawater component with δ65/63CuNIST976 ∼ 0.7 ‰ and δ66/64ZnJMC-Lyon ∼ 1.2 ‰. These values are fractionated from modern dissolved Cu and Zn by a factor of −0.3 ‰ and 0.5 ‰ respectively. We suggest that the deep Southern Pacific Ocean received sustained hydrothermal input during the last 6 Ma, which was recorded in the Cu and Zn isotope composition of Fe-Mn crusts precipitated thousands of kilometers away. Our study highlights that hydrothermal venting may be a significant source of Cu and Zn in the deep oceans despite their extensive precipitation within hydrothermal vent fields. We show that this source could be persistent through time, and thus, it could have a significant impact on the biogeochemical cycling of Cu and Zn in seawater which would ultimately be recorded by Fe-Mn crusts.

Baseline distribution of stable copper isotope compositions of the brain and other organs in mice.

Copper (Cu) stable isotopes are useful for understanding pathways and tracing changes in Cu homeostasis, such as those induced by various diseases (e.g. liver cirrhosis, numerous forms of cancer, and neurodegenerative diseases). However, this utility relies on a baseline understanding of the natural distribution of Cu isotopes between organs of healthy organisms, which is not well-known at present. Here, the distribution of natural Cu isotopes in the brain, liver, red blood cells, plasma, kidneys, and muscle of 14 mice (7 males and 7 females) from three different genetic backgrounds is assessed. We show that the Cu isotopic composition of most mouse organs is isotopically distinct from one another. The most striking feature is the heavy isotope enrichment of the kidney (δ65Cu=1.65±0.06‰, 2SE), brain (δ65Cu=0.87±0.03‰, 2SE) and liver (δ65Cu=0.71±0.24‰, 2SE) compared to blood components, i.e. red blood cells (RBCs) (δ65Cu=0.30±0.06‰, 2SE), and plasma (δ65Cu = -0.61±0.08‰, 2SE), with δ65Cu being the per mil deviation of the 65Cu/63Cu ratio from the NIST SRM 976 standard. Differences in genetic background do not appear to affect the isotopic distribution of Cu. Interestingly, male and female mice appear to have different Cu concentrations and isotopic compositions in their brain, plasma, muscle, and RBC. By demonstrating that organs have distinct isotopic compositions, our study reinforces the notion that Cu stable isotopes can be used to trace changes in homeostasis in diseases affecting Cu distribution, such as Alzheimer's disease, liver cancer, and possible chronic kidney failure.

An improved calibrated mass spectrometry for absolute copper isotope-ratio measurement using two strategies for mass bias correction factor

Modern advances in multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) have greatly promoted the investigation of copper isotopes in various research fields. To meet the demand, an improved calibrated mass spectrometry for the absolute determination of copper isotopic composition was developed in this study. The method has made progress in the investigation of instrumental mass bias correction factor for copper isotopic analysis using MC-ICPMS through employing two independent strategies. One is the conventional mathematical iterative method based on the MC-ICPMS measurement data; the other one is direct calculation using the absolute copper isotopic compositions in isotopically enriched 63Cu and 65Cu materials by developing a TE-TIMS method. The results of Kiter = 0.95563(16)k = 1 and KTE = 0.95551(17)k = 1 were consistent in their standard uncertainties, demonstrated the first cross-validation of these two strategies. Thereafter, the proposed calibrated mass spectrometry were applied to re-measure the copper isotope amount ratios in three isotopic reference materials, resulted in RNIST SRM 97665/63 = 0.44547(16)k = 2, RERM®−AE63365/63 = 0.44549(16)k = 2, and RERM®−AE64765/63 = 0.44557(16)k = 2, respectively. These expended uncertainties were only one third or one fifth of the stated uncertainties in their certificates. Furthermore, the absolute copper isotopic compositions in four natural-abundance samples and a new copper isotopic reference material GBW04624 were determined, given an average atomic weight of copper as Ar(Cu) = 63.5456(4)k = 2. The δ65Cu values of GBW04624 relative to NIST SRM 976, ERM®-AE633 and ERM®-AE647 were also applied by implementing the C-SSBIN calibration model. This provides an additional independently certified and SI-traceable copper isotopic reference material, in support of various scientific researches.