Zinc Isotopes Research Articles

The Validity of Extrinsic Stable Isotopic Labeling for Mineral Absorption Studies in Rats

The use of extrinsic stable and radioisotopic labels (Fe, Zn, Cu and Se) was compared with the use of intrinsic labels by measuring label retention in rats. Saccharomyces cerevisiae (Hansen strain CBS 1171) was prepared intrinsically enriched with a stable isotope of iron, zinc, copper or selenium, and unenriched freeze-dried yeast was extrinsically labeled with the appropriate stable and/or radioisotope. Male Wistar rats, weighing 80–100 g and fed a purified diet, were given a test meal of one of the above labeled yeasts. Isotopic retention was determined by fecal monitoring. Retention of the stable isotopes was determined by thermal ionization quadruple mass spectrometry (TIQMS) and retention of the radioisotopes by counting feces in a whole-body counter. The results indicated that the behavior of the labels differed among the minerals, with copper as the only one in which the intrinsic and extrinsic stable isotopes were comparably retained. With zinc, retention of the extrinsic radiolabel and intrinsic label was similar, but retention of the extrinsic stable isotope label was higher. With iron, the intrinsic label had a significantly lower retention than the two extrinsic labels; with selenium, retention of all three labels was different, but these differences were not of a sufficient magnitude to conclude that extrinsic stable isotopic labeling is not valid. These results demonstrate that an extrinsic stable isotope label can be used for copper, selenium and inorganic iron, but that such a label is not valid for studies on zinc.

Zinc isotope fractionation during mid-ocean ridge basalt differentiation: Evidence from lavas on the East Pacific Rise at 10°30′N

Zinc (Zn) isotope data for mid-ocean ridge basalts (MORB) are scarce. The possible effects of MORB differentiation and mantle compositional heterogeneity on MORB Zn isotope compositions are poorly understood. In this paper, we report Zn isotope data of MORB lavas from the East Pacific Rise (EPR) at 10°30′N, which are understood to have been derived by a similar extent of melting from a compositionally uniform mantle source but manifest significantly varying extents of magma differentiation (MgO = 7.38–1.76 wt%) to demonstrate unequivocal Zn isotope fractionation during MORB differentiation. These lavas have a small δ66Zn (relative to the JMC-Lyon standard) range of 0.21–0.32‰, with an average of 0.26 ± 0.07‰ (2SD, N = 24), overlapping with literature data. However, δ66Zn values show significant correlations with indices of magma differentiation (e.g., MgO and CaO), with the more differentiated samples having isotopically heavier Zn. We can thus conclude that MORB differentiation can lead to ∼0.1‰ δ66Zn elevation, which is similar to that observed in Hawaiian Kilauea Iki lava lake samples. Fractional crystallization of olivine and clinopyroxene at MgO > ∼3.5 wt% and clinopyroxene and Fe–Ti oxides dominated by ilmenite at MgO < ∼3.5 wt% results in the observed Zn isotope fractionation. The δ66Zn values for primitive N-MORB and MORB source mantle are estimated to be ∼0.22‰ and ∼0.17‰, respectively. Furthermore, we observe a positive correlation between δ66Zn and [La/Sm]N in primitive (MgO = 7.58–9.01 wt%) literature MORB, indicating the existence of possible Zn isotope heterogeneity in the oceanic upper mantle. We thus predict heavy Zn isotope enrichment in mantle sources for E-MORB samples with high [La/Sm]N, which requires future testing.

Kinetic zinc isotope fractionation in olivine phenocrysts records magma evolution history of intra-plate basalts

In the past few years, zinc isotope systematics of basaltic magmas have been widely used as novel proxies for terrestrial mantle heterogeneity induced by recycled crustal materials and for planet formation and evolution. The influence of crystal-melt isotope disequilibrium during magma differentiation on the zinc isotopic composition of basaltic melts, nonetheless, has received little attention. In addition, no quantitative constraint has yet been given for the diffusion-driven Zn isotope fractionation between olivine crystals and melts. Here we present high-precision zinc isotope data (δ66ZnJMC-Lyon) for a series of olivine phenocrysts separated from intra-plate alkali basalts from the Jiaodong Peninsula in Eastern China, together with in-situ chemical analysis. Olivine phenocrysts have Zn isotopic compositions which are too light in comparison with the host basaltic melts (Δ66Znol-melt = −0.41‰ to −0.10‰; n = 16) to be explained by equilibrium isotope fractionation at magmatic temperatures. Instead, the decrease of δ66Zn values with decreasing Mg# (i.e., Mg/[Mg + Fe2+] × 100) and increasing Zn + Fe2+ contents in olivine phenocrysts suggests diffusion-driven kinetic fractionation during olivine crystallization. The data is well-fitted with a diffusion model in which Zn together with Fe2+ diffuse from surrounding melt into olivine crystals and approximately equal flux of Mg diffuses into melt due to the large chemical gradient, yielding a kinetic Zn isotope fractionation factor βZn of 0.07. By utilizing the fractional crystallization model under equilibrium or disequilibrium conditions, it is suggested that diffusion-induced isotope disequilibrium during olivine crystallization may drive Zn isotopic composition of the residual melt toward heavier values. When using zinc isotope systematics of any basaltic magma to probe the source heterogeneity, this impact must be taken into account if the Zn isotope disequilibrium widely exists in olivine phenocrysts. Based on the time-related quantitative diffusion model, our results show that the magma residence time for strongly alkali basaltic lavas (∼20 days) is 10–60 times shorter than that for weakly alkali basaltic lavas (6 months to 4 years). This supports the generation of weakly alkali basalts via interaction between silica-undersaturated melts and the surrounding lithospheric mantle, implying a probable common mechanism in intra-plate basalts that could be comparable globally. Thus, Zn isotope disequilibrium between olivine crystals and melts could provide valuable information on the evolution history of intra-plate basaltic magmas.

Copper and Zinc isotopes trace the evolution of the Ediacara-Early Cambrian paleo-ocean redox condition in the Tarim Basin, China

The Ediacaran-early Cambrian transition is a critical period in the Earth's evolutionary history. A series of important geological and biological events are likely related to environmental change. Ocean oxygenation levels during the early Cambrian are still controversial and barely constrained although abundant geochemical studies have been conducted. The black shale widely developed in the Early Cambrian can record paleo-environmental information of contemporaneous seawater. The early Cambrian Yuertusi Formation black shale in the Luntan 3 well from the Tarim Basin was studied in terms of Cu and Zn isotopic composition and redox sensitive trace element to improve the knowledge of the extent of ocean oxygenation during the Ediacaran-Early Cambrian. The Yuertusi Formation is divided into four stages according to lithology variation and records of Cu and Zn isotopes and redox sensitive elements, indicating the fluctuation of ocean redox condition. The total organic carbon (TOC) varied widely from 0.10% to 18.25% with an average of 6.34%. Enrichment of Mo, U and V elements which have a synergistic relationship with TOC and redox proxies (ratios of U/Th and V/Cr, EF(Mo)-EF(U)) of the four stages in the Yuertusi Formation, indicate an anoxic even euxinic deposition environment, especially in stages Ⅰ and Ⅲ. Most of the Cu isotope values, lower than the modern seawater values, also indicate that the ocean state was anoxic and did not reach the current ocean oxidation level, which shows the same characteristics as the other profiles in different areas. The variation in the Cu isotope ranges from −3.10‰ to +1.23‰, and the Zn isotope ranges from 0.09‰ to 1.46‰. Relatively large Cu and Zn isotopic fractionation in stages Ⅰ and Ⅲ occur with an intense reduction environment, which is attributed to the combination of sulfide deposits that are eventually immobilized in sediments. Under the overall background of an anoxic environment, the four stages show a cycle of relative anoxic-weak oxidation-anoxic-weak oxidation, which is inferred to be connected with the transgressive-regressive cycle and weathering enhancement variation based on Ce anomaly, Mo/Toc ratios and C stable isotope data. The Early Cambrian transgression provided an anoxic even euxinic environment conducive to organic matter preservation for the development of black shale during stage Ⅰ. With the sea level fluctuation and weathering enhancement, the sea retreated gradually, productivity gradually increased, and the marine environment was relatively oxidized. The increasing trend of the whole Cu and Zn isotope values from bottom to top in the Yuertusi Formation is interpreted to be gradual relative oxidizing.

Nucleosynthetic isotope anomalies of zinc in meteorites constrain the origin of Earth's volatiles.

Material inherited from different nucleosynthesis sources imparts distinct isotopic signatures to meteorites and terrestrial planets. These nucleosynthetic isotope anomalies have been used to constrain the origins of material that formed Earth. However, anomalies have only been identified for elements with high condensation temperatures, leaving the origin of Earth's volatile elements unconstrained. We determined the isotope composition of the moderately volatile element zinc in 18 bulk meteorites and identified nucleosynthetic zinc isotope anomalies. Using a mass-balance model, we find that carbonaceous bodies, which likely formed beyond the orbit of Jupiter, delivered about half of Earth's zinc inventory. Combined with previous constraints obtained from studies of other elements, these results indicate that ~10% of Earth's mass was provided by carbonaceous material.

The geochemistry of zinc and copper stable isotopes in marine hydrothermal brine pools: Perspectives from metalliferous sediments of the Atlantis II Deep, Red Sea

This study provides a zinc and copper stable isotope characterization (δ66Zn, δ68Zn, and δ65Cu) of metalliferous seafloor sediments from the Atlantis II Deep, a hydrothermally influenced brine basin in the Red Sea. Samples collected from box cores that capture the entire stratigraphy in the Deep have δ66Zn and δ65Cu values of −0.31 to 0.34 ‰ (0.02 ‰ median) and − 1.81 to 1.02 ‰ (−0.34 ‰ median) relative to the JMC-Lyon and NIST SRM 976 standards, respectively. These results suggest enrichments of light stable isotopes in sediments compared to the hydrothermal inputs to the basin, which likely overlap the mantle-like isotopic signatures of basalts beneath the Deep. Such shifts to lower δ66Zn and δ65Cu values are consistent with widespread metal sulfide deposition from the brines because sulfide anions preferentially consume the light stable isotopes of zinc and copper. However, this interpretation contrasts with observations in the open ocean, where the fractionation of zinc and copper stable isotopes is strongly influenced by biological utilization and organic matter. Previous studies proposed that metal deposition in the Atlantis II Deep is also driven by adsorption onto iron oxides/hydroxides and their weakly crystalline (Si-)Fe-OOH precursor phases within the brines. However, because this process should accumulate heavy zinc and copper stable isotopes, its influence on isotopic fractionation is likely limited. Controls by metal sulfide precipitation are also indicated by spatial covariations between δ66Zn and concentrations of zinc and copper, that is, δ66Zn values increase whereas metal contents decrease with distance away from hydrothermal venting. Comparable trends are lacking for copper isotopes, perhaps because of additional influence by redox processes or, compared to zinc, a much stronger influence by adsorption onto (Si-)Fe-OOH phases, particularly in areas distal to hydrothermal venting where reduced sulfur could be scarce. Collectively, our results from the Atlantis II Deep indicate that zinc and copper stable isotopes could provide information about base and precious metals deposits from similar paleoenvironments. Firstly, zinc and copper stable isotopes shed light on metal sourcing and accumulation processes. Secondly, mineral precipitation in hydrothermally influenced brine pools produces zinc stable isotope patterns that, at least theoretically, could be of interest in mineral exploration at sub-basin and deposit scales.

Chemometrics-assisted inductively coupled plasma-optical emission spectrometry method for determination of natural zinc isotopes

Chemometrics-assisted inductively coupled plasma-optical emission spectrometry method for determination of natural zinc isotopes

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.

In VitroAnticancer Activity of the Light Stable Zinc Isotope (64Zn) Compounds

Today, stable isotopes of zinc are actively used for diagnostic purposes in oncology. However, there is extremely limited data on the attempts to apply stable zinc isotopes in cancer therapy or about the molecular mechanisms of their effects on the biology of tumor cells. Therefore, in this in vitro research, we evaluated the cytotoxic activity of stable zinc isotope (64Zn) enriched compounds against malignant cells and determined the mechanisms of their action. Malignant and non-malignant cells of different histogenesis were used as objects of the study. The effect of the Zn64aspartate, Zn64glutamate, and Zn64sulfate on cell viability in a comparative aspect was evaluated. Compounds containing 64Zn stable isotope enriched to 99.2%. Western blot analysis was used to determine the expression level of apoptosis regulatory proteins. Salts of 64Zn with amino acids had the most significant cytotoxic effect on malignant cells. The studied tumor cells, and especially MB16 melanoma cells were the most sensitive to the cytotoxic effects of Zn64aspartate. Zn64aspartate showed more significant cytotoxic activity than Zn aspartate (with natural isotope distribution) in the studied cell models. Zn64aspartate induced caspase-dependent cell death in A-549 cells and the p53-mediated apoptosis in melanoma cells. Malignant cells were more sensitive to the cytotoxic effect of the Zn64aspartate than normal cells. An increase in the intracellular concentration of 64Zn, and hence isotope mass balance changes, may lead to the suppression of the viability and proliferation of malignant cells. These results can become the basis for developing a new generation of anticancer drugs.

A Neandertal dietary conundrum: Insights provided by tooth enamel Zn isotopes from Gabasa, Spain

The characterization of Neandertals' diets has mostly relied on nitrogen isotope analyses of bone and tooth collagen. However, few nitrogen isotope data have been recovered from bones or teeth from Iberia due to poor collagen preservation at Paleolithic sites in the region. Zinc isotopes have been shown to be a reliable method for reconstructing trophic levels in the absence of organic matter preservation. Here, we present the results of zinc (Zn), strontium (Sr), carbon (C), and oxygen (O) isotope and trace element ratio analysis measured in dental enamel on a Pleistocene food web in Gabasa, Spain, to characterize the diet and ecology of a Middle Paleolithic Neandertal individual. Based on the extremely low δ66Zn value observed in the Neandertal's tooth enamel, our results support the interpretation of Neandertals as carnivores as already suggested by δ15N isotope values of specimens from other regions. Further work could help identify if such isotopic peculiarities (lowest δ66Zn and highest δ15N of the food web) are due to a metabolic and/or dietary specificity of the Neandertals.

Zinc isotope fractionation in mantle rocks and minerals, and a revised δ66Zn value for the Bulk Silicate Earth

The isotope composition of zinc (Zn) can be an important tracer of planetary formation and differentiation, but estimates of the Bulk Silicate Earth (BSE) and the extent and origin of Zn isotope variations in the mantle continue to be debated. We report 153 high-precision Zn isotope analyses of whole-rock samples and minerals of well-characterized, mantle-derived spinel and garnet peridotites from five sites in Siberia, Mongolia and China: 38 xenoliths in basaltic rocks (fertile to strongly melt-depleted as well as variably metasomatized or veined peridotites) and 3 orogenic peridotites. Data quality was rigorously tested by twenty-two duplicated analyses using several dissolution techniques. Spinel (Sp) contains 760–1460 μg/g Zn and hosts up to 58 % of whole-rock Zn budget in the peridotites followed by olivine (Ol, 30–66 % of whole-rock Zn budget), orthopyroxene (Opx), clinopyroxene (Cpx) and garnet, with abundance ratios of [Zn]Sp/[Zn]Ol = 15–47, [Zn]Ol/[Zn]Opx = ∼1.5, [Zn]Ol/[Zn]Cpx = ∼6. Spinel has higher δ66Zn values than coexisting silicates (∼0.12 ‰ higher than in Ol). Minerals in orogenic peridotites show disequilibrium Zn element and isotope partitioning due to slow inter-grain Zn diffusion at retrograde metamorphism.Fertile peridotites (≥3 wt% Al2O3) contain 52–60 μg/g Zn, usually higher than melt-depleted (<3 wt% Al2O3) rocks (40–53 μg/g). The δ66Zn values in the majority of spinel and garnet peridotites range from 0.11 to 0.26 ‰ and show no systematic co-variations with melt extraction indices (e.g., Al2O3, Mg#), suggesting, unlike some previous studies, that partial melting does not appreciably affect Zn isotope composition of residual mantle. Garnet lherzolites yield an average δ66Zn of 0.22 ± 0.09 ‰ (2SD), similar to that (0.18 ± 0.07 ‰, 2SD) for shallower spinel peridotites, indicating uniform Zn isotope composition with depth. Four fertile lherzolites from earlier work, duplicated in this study to assess inter-laboratory bias, fall in the same δ66Zn range, suggesting that previously reported higher δ66Zn for these samples could be due to analytical problems. We thus estimate the δ66Zn of the BSE at 0.19 ± 0.08 ‰ (2SD) based on suitable fertile peridotites from several localities in this study and the literature.The δ66Zn values (−0.10 to 0.04 ‰) are much lower in Fe-rich (9.3–13.1 wt% FeOT) and veined spinel peridotites as well as in spinel pyroxenite veins from Mongolia (−0.20 to 0.11 ‰). The Fe-rich peridotites and pyroxenites are rich in Zn (up to 113 μg/g) and were previously found to have anomalously low δ56Fe (−0.33 to − 0.27 ‰) and δ53Cr (−1.36 to − 0.05 ‰). We attribute these features to kinetic isotope fractionation during reaction with mafic melts migrating in conduits in the lithospheric mantle or intrusion of Fe-Zn-rich melts with light Fe-Zn isotope compositions. Kinetic Zn isotope fractionation, rather than equilibrium partial melting, may be a major cause of Zn isotope heterogeneity in the mantle.

The cadmium and zinc isotope compositions of the silicate Earth – Implications for terrestrial volatile accretion

Zinc and Cd isotope compositions are presented for a comprehensive suite of terrestrial rocks to constrain the extent of Zn and Cd isotope fractionation during igneous processes and better define the δ66Zn and δ114Cd values of the silicate Earth (the δ values denote per mille deviations of 66Zn/64Zn from JMC Lyon Zn and of 114Cd/110Cd from NIST SRM 3108 Cd). Analyses of spinel lherzolites provide a bulk silicate Earth (BSE) δ114CdBSE value of –0.06 ± 0.03 ‰ (2SD). For Zn, the peridotite data of the current and previous studies define a mean δ66ZnBSE = 0.20 ± 0.05 ‰ (2SD). Komatiite analyses of this and published investigations yield similar mean values, which suggests that the Zn and Cd isotope compositions of the mantle remained fairly constant since the Archean. Data for loess provide upper continental crust compositions of δ114Cd = 0.03 ± 0.10 ‰ and δ66Zn = 0.23 ± 0.07 ‰. The Zn isotope and abundance data for peridotites and oceanic basalts are in accord with the previous observation of a mantle array, with basalts having higher Zn concentrations and δ66Zn values than the peridotites. To a first order, this reflects slightly incompatible behaviour of Zn during mantle melting and melt differentiation with associated enrichment of heavy Zn isotopes in the melt phase. Cadmium is marginally more incompatible than Zn during igneous processes and the oceanic basalts also display a minor enrichment of heavy Cd isotopes relative to peridotites. However, secondary processes produce significant Cd isotope variability in both mantle melts and peridotites, obscuring the primary igneous array. The δ66ZnBSE estimates of this and previous studies resemble the Zn isotope compositions of CV and CO carbonaceous and some enstatite chondrites. In contrast, the BSE has a lower δ114CdBSE value than enstatite and carbonaceous chondrites. This implies that the Cd isotope composition of the BSE was either fractionated during accretion or that Earth’s Cd inventory was not exclusively acquired from material related to carbonaceous and enstatite chondrites. Importantly, delivery of Zn and Cd to the BSE solely by CI and CM chondrites is not in accord with the meteorite and terrestrial stable isotope data of these elements.

Recycling of carbonates into the deep mantle beneath central Balkan Peninsula: Mg-Zn isotope evidence

Magnesium (Mg) and zinc (Zn) isotopes have been applied to trace whether surface carbonates have been recycled into the deep mantle beneath Balkan Peninsula, where a stagnant slab exists in the mantle transition zone. Here we investigate a suite of Cenozoic sodic alkaline basaltic rocks (Na2O/K2O > 1), called the East Serbian Mafic Alkaline Rocks (ESMAR) from East Serbia in central Balkan Peninsula, which is an important segment of the Tethyan orogenic belt. The ESMAR have lower δ26MgDSM-3 (−0.49‰ to −0.39‰; n = 21) and higher δ66ZnJMC 3-0749L (0.35‰ to 0.45‰; n = 21) than those of normal mantle-derived melts (e.g., mid-oceanic ridge basalts; MORBs; δ26Mg = −0.25 ± 0.06‰ and δ66Zn = 0.27 ± 0.06‰). After excluding the effects of low-T and magmatic processes, the Mg and Zn isotopic anomalies of the ESMAR are proposed to have been caused by recycled carbonates in their mantle sources. The significantly low Zn contents, Zn/Fe and Fe/Mn ratios of the ESMAR indicate a highly depleted peridotitic mantle source. Their major element compositions (e.g., low Ti2O and high CaO/Al2O3) are consistent with those of experimental partial melts of “peridotite + CO2”. The incremental batch melting and end-member mixing models suggest that ∼5–10% of Mg-rich carbonates (dolomite and magnesite) have been recycled into the mantle sources of the ESMAR. Our results provide evidence for deep recycling of carbonates related to subduction of a Tethyan oceanic slab, most likely into the mantle transition zone beneath the Balkan Peninsula. This contributes a significant part of global deep carbon cycling during the Cenozoic.

Improvement of Digestion and Purification Steps for the Determination of Soil Zn Isotopes by MC‐ICP‐MS

Despite the determination of zinc (Zn) isotope in soil being undertaken by several laboratories worldwide, sample preparation steps are varied due to diverse soil properties and compositions. This paper proposes a widely applicable soil acid digestion procedure that has been thoroughly evaluated for both soil and geological reference materials. To ensure the general applicability of this method to large varieties of soil samples, synthetic multi‐element solutions of high matrix element: Zn ratios (M/Zn) were prepared by embracing all possible elemental compositions of forty‐three certified reference materials; the chemical preparation procedure was then tested and optimised using these synthetic solutions. Results show that the recovery rate of Zn could reach 99–100% after the pre‐treatment. Based on this method, the δ66/64Zn data relative to JMC‐Lyon 3‐0749L Zn of previously uncharacterised NIST reference materials (including SRM 2709a San Joaquin soil, SRM 2710a Montana Soil and SRM 2711 Montana Soil) and Chinese certified reference materials (GSS‐1a, GSS‐7a, GSS‐5, GSS‐8, GSS‐14, GSS‐18, GSS‐20, GSS‐24, GSS‐31) were measured using MC‐ICP‐MS with a range from ‐0.08‰ to 0.35‰. The Zn isotope compositions of twenty‐nine soil samples from twenty‐one provinces/municipalities across China were also analysed and were found to fall within typical ranges from ‐0.09‰ to 0.28‰. The intermediate precision of several pure Zn standard solutions was better than ± 0.05‰ (2s) over 22 months of measurement. This method and results are useful for comparison and calibration of data between laboratories as well as providing a solid reference soil dataset for future studies dealing with Zn isotopes.

Environmental implications of land use change on the fate of Zn in agricultural soils: A case study of Puding karst soils, southwest China

Land use change threatens food security because it may cause the depletion and/or low bioavailability of micronutrients in agricultural soils. Therefore, it is significant to investigate the fate of micronutrients and predict the potential environmental problems. The zinc isotope technique is of particular interest in interpreting soil processes. In this study, Zn isotopic data of soil samples in five profiles based on different land uses were provided, and Zn behavior in different soils was discussed. The isotopic ratios of soil samples in the abandoned orchard, secondary forest, abandoned cropland, and cropland are similar, with the δ66Zn varying from 0.15 to 0.29‰. However, the samples in shrub grassland show a lower δ66Zn of 0–0.20‰, which may be affected by anthropogenic sources. For the vertical patterns, the non-cultivated long-rooted plants (i.e., abandoned orchard and secondary forest) show no significant difference in the distribution of δ66Zn, but the patterns of cropland and abandoned cropland samples are reversed. The cropland samples show positive correlations between δ66Zn and Fe2O3 (R2 = 0.90) and MnO (R2 = 0.75), indicating that Fe and Mn oxides preferentially adsorb heavy Zn isotopes on the mineral surfaces. The high affinity between Zn and oxides indicated that the concentration of bio-available Zn in cropland soils was getting lower. As a result, the supplies of micronutrients may be deficient and urged from fertilizer. This study provides a better understanding of Zn cycling in agricultural systems and gives improvements in soil management.

Analysis of excitation functions of (p,n) reactions for the stable isotopes of zinc and copper up to 40 MeV

Analysis of excitation functions of (p,n) reactions for the stable isotopes of zinc and copper up to 40 MeV

Stable isotope (C, O, S, and Zn) geochemistry of marble-hosted exhalative zinc deposits in the Central Metasedimentary Belt, Grenville Province, Canada: Insights into ore deposition and tectonic setting

Mesoproterozoic marbles of the southwestern Grenville Province contain numerous stratiform zinc deposits, which include the world-class Balmat-Edwards Zn-Pb district in the Adirondack Lowlands and the Franklin-Sterling Zn-Fe-Mn district in the New Jersey Highlands. Ten small deposits in the Central Metasedimentary Belt (CMB) of Ontario and Quebec were selected for stable isotope study (C and O in carbonates and S and Zn in sulfides) to help constrain depositional conditions, ore genesis, and tectonic setting. These deposits and the Balmat-Edwards and Franklin-Sterling districts are interpreted to have formed in contemporaneous back-arc basins associated with rifting of the Andean-style margin of Laurentia. Stable isotope systematics and the geology of these deposits indicate two distinct sedimentary exhalative (Sedex) settings: marble-hosted deposits associated with volcanic rocks, and marble-hosted deposits that are not associated with volcanic rocks and sometimes occur with evaporites. Volcanic-associated Sedex deposits (the Long Lake, Slave Lake, Wilkinson, Lafontaine, Bouchette, and Leitch deposits, and the Franklin-Sterling district) have COS isotope systematics that are consistent with water/rock interaction between marine carbonate protoliths and fluids having an igneous component at ca. 150 ± 25 °C. In contrast, Sedex deposits not associated with volcanic rocks (the Cadieux, Spry, Thirty Island Lake, and Salerno Lake deposits, and the Balmat-Edwards district) have C and O isotope ratios that are consistent with formation at ambient or low (<80 °C) temperatures. Sulfur isotopes of sulfides in some evaporite-associated deposits are similar to those of other Proterozoic Sedex deposits (δ34S = 5–15 ‰ VCDT), with the Cadieux and Spry having lower values (δ34S ≈ 0‰) which might reflect differences in depositional settings. Zinc isotope ratios of CMB Zn deposits are relatively constrained (δ66Zn = 0.17 ± 0.04 ), and are similar to other seafloor deposits. An exception to this is the Thirty Island Lake deposit in the Frontenac terrane, which has δ66Zn = 0.46 ± 0.05 ‰, which may indicate an exotic origin relative to other CMB deposits. The recognition of the volcanic association for some Grenville Sedex deposits and not for others (and the relationship with evaporites for this group) has implications for Zn exploration programs in this region.

Zinc, sulfur and cadmium isotopes and Zn/Cd ratios as indicators of the origin of the supergiant Broken Hill Pb–Zn–Ag deposit and other Broken Hill-type deposits, New South Wales, Australia

AbstractVarious genetic models have been proposed for the supergiant Proterozoic Broken Hill Pb–Zn–Ag deposit largely based on geological and geochronological evidence. Here we present Zn, Cd and S isotope compositions as well as Zn/Cd ratios of sphalerite from Broken Hill and minor Broken Hill-type deposits (Australia) to help constrain these models but focus on syngenetic and magmatic–hydrothermal processes, since epigenetic models can be rejected because the orebodies were deformed and metamorphosed by the Olarian Orogeny. Values of δ34SVCDT, δ66ZnAA-ETHand δ114CdNIST SRM 3108for sphalerite from Broken Hill range from +0.27 to +4.73 ‰, −1.15 to +0.46 ‰ and −0.48 to +0.01 ‰, respectively, while those for the smaller Broken Hill-type deposits range from −5.11 to +1.28 ‰, −0.97 to +0.10 ‰ and −1.02 to +2.59 ‰, respectively. By combining published S isotope data of sulfides from the Broken Hill district with those obtained here, the sources of sulfur via thermochemical sulfate reduction, bacterial sulfate reduction and a magmatic origin cannot be distinguished. However, when the S isotope compositions are considered along with the broad range of Cd and Zn isotope data for sphalerite, which are among the lightest and heaviest yet reported for a sulfide deposit, the isotopic datasets are consistent with low-temperature biogenic processes associated with syngenetic deposition of sulfides. Cadmium isotope compositions when coupled with Zn/Cd ratios of sphalerite have previously been used to classify Pb–Zn deposits, including low-temperature, high-temperature and exhalative ores. However, the Zn/Cd ratios of sphalerite from Broken Hill cannot be used for such classification purposes.

Recycled carbonates in the mantle sources of natural kamafugites: A zinc isotope perspective

Abstract Kamafugites are strongly silica-undersaturated melts that are difficult to produce by partial melting of volatile-free peridotites but can be produced experimentally in the presence of CO2. Nevertheless, there is not yet direct evidence for a CO2-rich mantle source and the possible presence of recycled carbonates in the source of natural kamafugites. Marine carbonates have a heavier zinc isotopic composition (δ66Zn) than that of the mantle by up to 1.0‰, making zinc isotopes a sensitive tracer for recycled carbonates in the sources of mantle-derived magmas. Here we take Cenozoic kamafugites from the West Qinling orogen in China as an example to address the origin of this rare volcanic rock. The West Qinling kamafugites are strongly silica-undersaturated (SiO2 = 37.0 to 43.0 wt%) and have significantly higher δ66Zn (0.30‰ to 0.47‰) than that of the normal mantle (0.18 ± 0.05‰). No correlation between δ66Zn and MgO or SiO2 contents is observed, indicating that the high δ66Zn was not a result of magmatic differentiation. Modeling of melting indicates that even at extremely low degree (~0.5%), partial melting of a normal peridotitic source is still unlikely to produce silicate melts with δ 66Zn values exceeding 0.30‰. Thus, the elevated δ66Zn of the West Qinling kamafugites demonstrates the presence of recycled carbonates in their mantle sources. Binary-mixing modeling suggests that the source contains ~5 to 15% recycled carbonates, which is supported by the positive correlation between δ66Zn and CaO/Al2O3. Overall, the West Qinling kamafugites represent the products of low-degree partial melting of a recycled carbonate-bearing peridotite source, which provides evidence for an important role of recycled carbonates in the origin of natural kamafugite suites.

Zinc isotope anomalies in primitive meteorites identify the outer solar system as an important source of Earth's volatile inventory

The source of and timing of delivery of the volatile elements to Earth is a question that is fundamental to understanding how our planet evolved. Here, we show that primitive meteorites have resolved mass-independent Zn isotope anomalies from the terrestrial reservoir. Carbonaceous chondrites (CC), likely originating from the outer Solar System are distinct from non-CC, and Earth is intermediate between these two components. Modelling based on these data indicates that around 30% of Earth's budget of Zn and other moderately volatile material derives from the participation of 6% of CC-like materials during Earth's accretion, with the remaining coming from NC meteorites. This implies that, despite the relatively minor mass of Earth thought to derive from CC-like material, the CC component of Earth was relatively and significantly volatile-enriched; this is in line with the observation that the terrestrial elemental abundance pattern of moderately volatile elements could be explained by a carbonaceous source, and with the carbonaceous chondrite-like isotopic budget of more volatile-rich material accreted later in Earth's accretion history (e.g. Hg, Se, N, noble gases).