Zinc Isotopes Research Articles

Geology, isotope geochemistry and ore genesis of the Shanshulin carbonate-hosted Pb–Zn deposit, southwest China

The Shanshulin Pb–Zn deposit occurs in Upper Carboniferous Huanglong Formation dolomitic limestone and dolostone, and is located in the western Yangtze Block, about 270km west of Guiyang city in southwest China. Ore bodies occur along high angle thrust faults affiliated to the Weishui regional fault zone and within the northwestern part of the Guanyinshan anticline. Sulfide ores are composed of sphalerite, pyrite, and galena that are accompanied by calcite and subordinate dolomite. Twenty-two ore bodies have been found in the Shanshulin deposit area, with a combined 2.7milliontonnes of sulfide ores grading 0.54 to 8.94wt.% Pb and 1.09 to 26.64wt.% Zn. Calcite samples have δ13CPDB and δ18OSMOW values ranging from −3.1 to +2.5‰ and +18.8 to +26.5‰, respectively. These values are higher than mantle and sedimentary organic matter, but are similar to marine carbonate rocks in a δ13CPDB vs. δ18OSMOW diagram, suggesting that carbon in the hydrothermal fluid was most likely derived from the carbonate country rocks. The δ34SCDT values of sphalerite and galena samples range from +18.9 to +20.3‰ and +15.6 to +17.1‰, respectively. These values suggest that evaporites are the most probable source of sulfur. The δ34SCDT values of symbiotic sphalerite–galena mineral pairs indicate that deposition of sulfides took place under chemical equilibrium conditions. Calculated temperatures of S isotope thermodynamic equilibrium fractionation based on sphalerite–galena mineral pairs range from 135 to 292°C, consistent with previous fluid inclusion studies. Temperatures above 100°C preclude derivation of sulfur through bacterial sulfate reduction (BSR) and suggest that reduced sulfur in the hydrothermal fluid was most likely supplied through thermo-chemical sulfate reduction (TSR). Twelve sphalerite samples have δ66Zn values ranging from 0.00 to +0.55‰ (mean +0.25‰) relative to the JMC 3-0749L zinc isotope standard. Stages I to III sphalerite samples have δ66Zn values ranging from 0.00 to +0.07‰, +0.12 to +0.23‰, and +0.29 to +0.55‰, respectively, showing the relatively heavier Zn isotopic compositions in later versus earlier sphalerite. The variations of Zn isotope values are likely due to kinetic Raleigh fractional crystallization. The 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios of the sulfide samples fall in the range of 18.362 to 18.573, 15.505 to 15.769 and 38.302 to 39.223, respectively. The Pb isotopic ratios of the studied deposit plot in the field that covers the upper crust, orogenic belt and mantle Pb evolution curves and overlaps with the age-corrected Proterozoic folded basement rocks, Devonian to Lower Permian sedimentary rocks and Middle Permian Emeishan flood basalts in a 207Pb/204Pb vs. 206Pb/204Pb diagram. This observation points to the derivation of Pb metal from mixed sources. Sphalerite samples have 87Sr/86Sr200Ma ratios ranging from 0.7107 to 0.7115 similar to the age-corrected Devonian to Lower Permian sedimentary rocks (0.7073 to 0.7111), higher than the age-corrected Middle Permian basalts (0.7039 to 0.7078), and lower than the age-corrected Proterozoic folded basement (0.7243 to 0.7288). Therefore, the Sr isotope data support a mixed source. Studies on the geology and isotope geochemistry suggest that the Shanshulin deposit is a carbonate-hosted, thrust fault-controlled, strata-bound, epigenetic, high grade deposit formed by fluids and metals of mixed origin.

The magnetic isotope effect as a tool for apoptosis modulation in leukemic cells

Lymphocytes from healthy donors and leukemic cells of patients with acute B-lymphoblastic leukemia (BALL-1) and acute myeloid leukemia were exposed to nanoparticles bearing magnetic (Zn-67) and nonmagnetic (total isotope pool) nuclei of zinc. The values of the corresponding magnetic isotope effects determined as the ratio of LD50 magnitudes of preparations with magnetic and nonmagnetic zinc isotopes were 0, 3.5, and 1.5. Morphological studies using confocal and fluorescence microscopy showed apoptotic death of cells with the preparations; as well, there was an increase in the cell aggregation and better aggregation of nanoparticles in the case of 67Zn-NP, which resulted in a decrease of cytotoxicity. However the magnetic isotope effect was observed even in the case of aggregation.

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

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

A role for scavenging in the marine biogeochemical cycling of zinc and zinc isotopes

Zinc (Zn) and cadmium (Cd) are important biologically active trace-metals in the ocean. To date, the marine distributions of these elements have been understood primarily in terms of biological assimilation by growing phytoplankton and regeneration of sinking biological material. Initial studies of Zn and Cd concentrations and stable isotope ratios (δ66Zn and δ114Cd) have therefore focused on their use as simple tracers of assimilation and regeneration in the oceans. However, these two processes are insufficient to explain new data on the marine distribution of Zn and δ66Zn. Here, using the first high-resolution paired marine depth profiles of Zn, Cd, δ66Zn and δ114Cd, we suggest that scavenging of Zn onto organic matter plays a major, yet largely unconsidered, role in the marine cycling of Zn. This hypothesis is supported by culture experiments, which show that Zn released from degrading phytoplankton is rapidly scavenged back onto organic matter, and that adsorbed Zn is isotopically heavier than the dissolved phase by 0.58‰. In contrast, very little Cd or phosphate was scavenged and Cd isotopes were not significantly fractionated during degradation. Our hypothesis is further supported by one-dimensional modeling, which reproduces observed marine δ66Zn profiles with <1% of Zn adsorbed to particles. Understanding how Zn cycling in the oceans is a balance between assimilation, scavenging, and regeneration is necessary in order to investigate δ66Zn as a tracer of marine productivity. We anticipate that paired analyses of δ66Zn and δ114Cd will prove to be valuable new tools in constraining patterns of global primary productivity, providing key information for the marine carbon cycle during periods of past and present global climate change.

The results of the first photonuclear reaction performed in Turkey: the zinc example

We have investigated the decays of several zinc isotopes produced by photonuclear reactions, which were induced by bremsstrahlung photon beams from a clinical e-linac. A photon beam of 18 MeV endpoint energy was directed at a target consisting of primarily zinc isotopes in their natural abundances. Subsequently, the induced decays of unstable zinc isotopes were measured with an HPGe detector twice, once shortly after irradiation and once on the following day. Decays of Zn-63, Zn-65, Zn-69m, and Cu-67 were measured and fitted. In addition, the gamma energy levels of the daughters of these decays were measured with good accuracy. All of the measurements were consistent with established data within error bars.

Search for rare processes with ZnWO4crystal scintillators

Radiopure ZnWO4 crystal scintillators with mass (0.1–0.7 kg) have been developed and put inmeasurement in the Gran Sasso National Laboratories of the INFN to search for rare processes. The radioactive contamination of the crystals have been estimated and the double beta decay of zinc and tungsten isotopes was searched for, reaching a sensitivity at the level of 1018−1021 yr; in addition a new half-life limit on alpha transition of 183W to the metastable excited level of 179Hf has also been obtained. The achieved radiopurity of the ZnWO4 crystals make them very promising detectors for ββ decay investigations while their anisotropic features make them very interesting detectors to investigate dark matter particles directionality.

Zinc Isotope Fractionation during Early Dissolution of Biotite Granite

Stable metal isotopes show great promise as a novel technique to study fundamental processes underlying micronutrient dynamics in soils and uptake by plants in situ. An important step in the development of these isotope systems is to constrain the extent and mechanisms of the isotopic fractionation in the plant–soil environment. One of the prominent micronutrient sources that needs to be constrained is release from parent material. To this end, we tested the isotopic fractionation of Zn during the very early stages of proton- and ligand-controlled dissolution of a finely powdered, fresh biotite granite using batch experiments. The observed fractionation pattern was similar for both dissolution mechanisms (proton and ligand promoted). Isotope fractionations were highest in the early stages of dissolution and probably kinetically controlled. After a few days, isotope fractionation imparted isotopically light Zn in the soil solution.

Zinc isotope fractionation during surface adsorption and intracellular incorporation by bacteria

Zinc (Zn) isotopes are fractionated during biogeochemical processing by microorganisms. Uncertainties remain, however, regarding the roles of cell surface adsorption and speciation of aqueous Zn on the extents of isotopic fractionation. In this study, we conducted bacterial surface adsorption and intracellular incorporation experiments using Zn and representative Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas mendocina, Escherichia coli) bacterial species, as well as a natural bacterial consortium derived from soil. Under conditions of high Zn:bacteria ratio, surface complexes preferentially incorporated the heavier isotopes of Zn, resulting in an average Δ66Znadsorbed-solution of +0.46‰ (αadsorbed-solution≈1.00046). Adsorption experiments conducted under conditions of low Zn:bacteria ratio appear to have been complicated by the presence of dissolved organic exudates that competed with surface functional group sites for Zn. We were able to empirically model this process to show that very small amounts of Zn-organic complexes with fractionation factors in the range of α=1.002 to 1.003 could account for the observed δ66Zn of the experimental solutions. For the intracellular incorporation experiments, the presence of 0.2 and 2mg/L of Zn (as Zn-citrate) resulted in a Δ66Znincorporated-solution ranging from −0.2‰ to +0.5‰, depending upon the bacterial species and the growth phase. The addition of 0.2 and 2mg/L Zn2+ to the growth medium appeared to create a metal stress response (or at least a change in metal processing) in P. mendocina that resulted in a positive Δ66Znincorporated-solution of up to +2.04‰. Our study suggests that Zn isotopes have the potential to be used to elucidate metal-binding pathways associated with microorganisms in natural systems, but that the interpretation of these effects is likely complicated by factors such as competing surface interactions and differences in bacterial species and metal speciation.

Zinc, sulfur and lead isotopic variations in carbonate-hosted Pb–Zn sulfide deposits, southwest China

The Sichuan–Yunnan–Guizhou Pb–Zn metallogenic province in the western Yangtze Block, southwest China, contains more than four hundred Pb–Zn deposits with more than 200milliontons of Pb–Zn ores at mean grades of 5wt.% Pb and 10wt.% Zn. These deposits are hosted in Sinian (Ediacaran) to Permian carbonate rocks and are structurally controlled by thrust fault–fold structures, and are spatially associated with the late Permian~260Ma Emeishan flood basalts. Two representative low temperature hydrothermal Pb–Zn sulfide deposits, the Tianqiao and Banbanqiao deposits in the southeastern part of the Sichuan–Yunnan–Guizhou Pb–Zn metallogenic province are selected for Zn–S–Pb isotopic analyses. Sphalerite from the Tianqiao deposit has δ66Zn values ranging from −0.26 to +0.58‰ relative to the JMC 3–0749L zinc isotope standard, whereas δ66Zn values of sphalerite from the Banbanqiao deposit range from +0.07 to +0.71‰. The zinc isotopic composition of sphalerite from both deposits increase from early to final mineralization stage. In addition, sphalerite from the center (near to bottom) part of the No. 1 ore body in the Tianqiao deposit has lower δ66Zn values (−0.01 to +0.43‰) than those (+0.11 to +0.57‰) in the periphery (near to top). Sinian to Permian sedimentary rocks and Permian Emeishan flood basalts, the potential zinc metal source rocks, have δ66Zn values range from −0.24 to +0.17‰ and from +0.32 to +0.44‰, respectively. The majority of the hydrothermal sphalerite has heavier zinc isotope than the country rocks, precluding the mixing of multiple zinc sources as the key factor controlling the spatial and temporal variations of zinc isotope. Therefore, the increased δ66Zn values from the early to late stage and from the center to top could be due to kinetic Raleigh fractionation. Sphalerite from the Tianqiao and Banbanqiao deposits has δ34S values ranging from +10.9 to +14.8‰ and from +3.9 to +9.0‰, respectively, lower than Cambrian to Permian marine sulfates (+15 to +35‰) and sulfate-bearing evaporates (+15 to +28‰) in the Devonian to Permian carbonate host rocks. Sulfur of the Pb–Zn ores from both deposits is interpreted as the result of thermal chemical sulfate reduction of evaporates in the sedimentary rocks, most likely the host rocks. Sphalerite from the Tianqiao deposit has Pb isotope similar to that of age-corrected Devonian to Permian carbonate host rocks, whereas sphalerite from the Banbanqiao deposit has Pb isotope similar to that of age-corrected underlying Precambrian basement rocks. Therefore, at least lead in the Tianqiao and Banbanqiao deposits was mainly originated from the host rocks and the underlying basements, respectively. Zn–S–Pb isotopic studies of sphalerite from both deposits indicate that sources of metals and sulfur in the hydrothermal fluid for the Tianqiao deposit are the Paleozoic carbonate host rocks, whereas for the Banbanqiao deposit the sources are the Precambrian basements and the Paleozoic carbonate host rocks, respectively.

The oceanic mass balance of copper and zinc isotopes, investigated by analysis of their inputs, and outputs to ferromanganese oxide sediments

The oceanic biogeochemical cycles of the transition metals have been eliciting considerable attention for some time. Many of them have isotope systems that are fractionated by key biological and chemical processes so that significant information about such processes may be gleaned from them. However, for many of these nascent isotopic systems we currently know too little of their modern oceanic mass balance, making the application of such systems to the past speculative, at best. Here we investigate the biogeochemical cycling of copper (Cu) and zinc (Zn) isotopes in the ocean. We present estimates for the isotopic composition of Cu and Zn inputs to the oceans based on new data presented here and published data. The bulk isotopic composition of dissolved Cu and Zn in the oceans (δ65Cu ∼+0.9‰, δ66Zn ∼+0.5‰) is in both cases heavier than their respective inputs (at around δ65Cu=+0.6‰ and δ66Zn=+0.3‰, respectively), implying a marine process that fractionates them and a resulting isotopically light sedimentary output. For the better-known molybdenum isotope system this is achieved by sorption to Fe–Mn oxides, and this light isotopic composition is recorded in Fe–Mn crusts. Hence, we present isotopic data for Cu and Zn in three Fe–Mn crusts from the major ocean basins, which yield δ65Cu=0.44±0.23‰ (mean and 2SD) and δ66Zn=1.04±0.21‰. Thus for Cu isotopes output to particulate Fe–Mn oxides can explain the heavy isotopic composition of the oceans, while for Zn it cannot. The heavy Zn in Fe–Mn crusts (and in all other authigenic marine sediments measured so far) implies that a missing light sink is still to be located. These observations are some of the first to place constraints on the modern oceanic mass balance of Cu and Zn isotopes.

A new method for precise determination of iron, zinc and cadmium stable isotope ratios in seawater by double-spike mass spectrometry

The study of Fe, Zn and Cd stable isotopes (δ56Fe, δ66Zn and δ114Cd) in seawater is a new field, which promises to elucidate the marine cycling of these bioactive trace metals. However, the analytical challenges posed by the low concentration of these metals in seawater has meant that previous studies have typically required large sample volumes, highly limiting data collection in the oceans. Here, we present the first simultaneous method for the determination of these three isotope systems in seawater, using Nobias PA-1 chelating resin to extract metals from seawater, purification by anion exchange chromatography, and analysis by double spike MC-ICPMS. This method is designed for use on only a single litre of seawater and has blanks of 0.3, 0.06 and <0.03ng for Fe, Zn and Cd respectively, representing a 1–20 fold reduction in sample size and a 4–130 decrease in blank compared to previously reported methods. The procedure yields data with high precision for all three elements (typically 0.02–0.2‰; 1σ internal precision), allowing us to distinguish natural variability in the oceans, which spans 1–3‰ for all three isotope systems. Simultaneous extraction and purification of three metals makes this method ideal for high-resolution, large-scale endeavours such as the GEOTRACES program.

Zinc isotope fractionation during magmatic differentiation and the isotopic composition of the bulk Earth

The zinc stable isotope system has been successfully applied to many and varied fields in geochemistry, but to date it is still not completely clear how this isotope system is affected by igneous processes. In order to evaluate the potential application of Zn isotopes as a proxy for planetary differentiation and volatile history, it is important to constrain the magnitude of Zn isotopic fractionation induced by magmatic differentiation. In this study we present high-precision Zn isotope analyses of two sets of chemically diverse, cogenetic samples from Kilauea Iki lava lake, Hawaii, and Hekla volcano, Iceland, which both show clear evidence of having undergone variable and significant degrees of magmatic differentiation.The Kilauea Iki samples display small but resolvable variations in Zn isotope composition (0.26‰<δ66Zn<0.36‰; δ66Zn defined as the per mille deviation of a sample's 66Zn/64Zn compositional ratio from the JMC-Lyon standard), with the most differentiated lithologies exhibiting more positive δ66Zn values. This fractionation is likely a result of the crystallization of olivine and/or Fe–Ti oxides, which can both host Zn in their crystal structures. Samples from Hekla have a similar range of isotopic variation (0.22‰<δ66Zn<0.33‰), however, the degree of fractionation caused by magmatic differentiation is less significant (only 0.07‰) and no correlation between isotope composition and degree of differentiation is seen. We conclude that high temperature magmatic differentiation can cause Zn isotope fractionation that is resolvable at current levels of precision, but only in compositionally-evolved lithologies. With regards to primitive (ultramafic and basaltic) material, this signifies that the terrestrial mantle is essentially homogeneous with respect to Zn isotopes. Utilizing basaltic and ultramafic sample analyses, from different geologic settings, we estimate that the average Zn isotopic composition of Bulk Silicate Earth is δ66Zn=0.28±0.05‰ (2s.d.).

A Zn isotope perspective on the rise of continents

Zinc isotope abundances are fairly constant in igneous rocks and shales and are left unfractionated by hydrothermal processes at pH<5.5. For that reason, Zn isotopes in sediments can be used to trace the changing chemistry of the hydrosphere. Here, we report Zn isotope compositions in Fe oxides from banded iron formations (BIFs) and iron formations of different ages. Zinc from early Archean samples is isotopically indistinguishable from the igneous average (δ(66) Zn ~0.3‰). At 2.9-2.7Ga, δ(66) Zn becomes isotopically light (δ(66) Zn<0‰) and then bounces back to values >1‰ during the ~2.35Ga Great Oxygenation Event. By 1.8Ga, BIF δ(66) Zn has settled to the modern value of FeMn nodules and encrustations (~0.9‰). The Zn cycle is largely controlled by two different mechanisms: Zn makes strong complexes with phosphates, and phosphates in turn are strongly adsorbed by Fe hydroxides. We therefore review the evidence that the surface geochemical cycles of Zn and P are closely related. The Zn isotope record echoes Sr isotope evidence, suggesting that erosion starts with the very large continental masses appearing at ~2.7Ga. The lack of Zn fractionation in pre-2.9Ga BIFs is argued to reflect the paucity of permanent subaerial continental exposure and consequently the insignificant phosphate input to the oceans and the small output of biochemical sediments. We link the early decline of δ(66) Zn between 3.0 and 2.7Ga with the low solubility of phosphate in alkaline groundwater. The development of photosynthetic activity at the surface of the newly exposed continents increased the oxygen level in the atmosphere, which in turn triggered acid drainage and stepped up P dissolution and liberation of heavy Zn into the runoff. Zinc isotopes provide a new perspective on the rise of continents, the volume of carbonates on continents, changing weathering conditions, and compositions of the ocean through time.

Is aging recorded in blood Cu and Zn isotope compositions?

Recent isotopic observations of animal samples indicate body accumulation of heavy zinc and light copper throughout life. This hypothesis has never been tested for humans, but the existence of a relationship between blood isotopic composition and age could be promising for age assessment methodologies. Dietary habits can also influence the blood zinc isotope composition, being an additional source of isotopic variation. In order to reduce this putative source of variation, we selected a population living in an isolated area (Sakha Republic, Russia) where diverse foods are of limited availability. We sampled blood from 8 male and 31 female Yakut volunteers between the ages of 18 and 74. Zinc, iron and copper were purified by liquid chromatography on ion exchange resin and their stable isotope ratios were measured using multiple-collector inductively coupled plasma mass spectrometry. According to observations of animal samples, the (66)Zn/(64)Zn ratio increases with age. We also observe that the (65)Cu/(63)Cu ratio decreases with age, whereas iron isotopic compositions are unrelated to age. The copper and zinc isotope compositions of the Yakut's blood are significantly lighter and heavier, respectively, than in samples of European and Japanese populations. The Yakut is a circumpolar population in which individuals have an elevated basal metabolic rate in response to cold stress. This elevated basal metabolic rate could enhance copper and zinc isotopic fractionation by accelerating the turnover of the copper and zinc stores.

Heterogeneous distribution of natural zinc isotopes in mice

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

Formation of a Low-Crystalline Zn-Silicate in a Stream in SW Sardinia, Italy

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

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

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

Zinc isotopic evidence for the origin of the Moon

Volatile elements have a fundamental role in the evolution of planets. But how budgets of volatiles were set in planets, and the nature and extent of volatile-depletion of planetary bodies during the earliest stages of Solar System formation remain poorly understood. The Moon is considered to be volatile-depleted and so it has been predicted that volatile loss should have fractionated stable isotopes of moderately volatile elements. One such element, zinc, exhibits strong isotopic fractionation during volatilization in planetary rocks, but is hardly fractionated during terrestrial igneous processes, making it a powerful tracer of the volatile histories of planets. Here we present high-precision zinc isotopic and abundance data which show that lunar magmatic rocks are enriched in the heavy isotopes of zinc and have lower zinc concentrations than terrestrial or Martian igneous rocks. Conversely, Earth and Mars have broadly chondritic zinc isotopic compositions. We show that these variations represent large-scale evaporation of zinc, most probably in the aftermath of the Moon-forming event, rather than small-scale evaporation processes during volcanism. Our results therefore represent evidence for volatile depletion of the Moon through evaporation, and are consistent with a giant impact origin for the Earth and Moon.

Galvanized lunacy

The finding that magmatic material from the Moon is more enriched in the heavy isotopes of zinc than its terrestrial and Martian analogues prompts fresh thinking about the origin of our natural satellite. See Letter p.376

Iron, zinc, magnesium and uranium isotopic fractionation during continental crust differentiation: The tale from migmatites, granitoids, and pegmatites

The causes of some stable isotopic variations in felsic rocks are not well understood. In particular, the origin of the heavy Fe isotopic compositions (i.e., high δ56Fe values, deviation in ‰ of the 56Fe/54Fe ratio relative to IRMM-014) of granites with SiO2>70wt.% compared with less silicic rocks is still debated. It has been interpreted to reflect isotopic fractionation during late stage aqueous fluid exsolution, magma differentiation, partial melting, or Soret (thermal) diffusion. The present study addresses this issue by comparing the Fe isotopic compositions of a large range of differentiated crustal rocks (whole rocks of migmatites, granitoids, and pegmatites; mineral separates) with the isotopic compositions of Zn, Mg and U. The samples include granites, migmatites and pegmatites from the Black Hills, South Dakota (USA), as well as I-, S-, and A-type granitoids from Lachlan Fold Belt (Australia). The nature of the protolith (i.e., I- or S-type) does not influence the Fe isotopic composition of granitoids. Leucosomes (partial melts in migmatites) tend to have higher δ56Fe values than melanosomes (melt residues) indicating that partial melting of continental crust material can possibly fractionate Fe isotopes. No clear positive correlation is found between the isotopic compositions of Mg, U and Fe, which rules out the process of Soret diffusion in the systems studied here. Zinc isotopes were measured to trace fluid exsolution because Zn can easily be mobilized by aqueous fluids as chloride complexes. Pegmatites and some granitic rocks with high δ56Fe values also have high δ66Zn values. In addition, high-SiO2 granites show a large dispersion in the Zn/Fe ratio that cannot easily be explained by magma differentiation alone. These results suggest that fluid exsolution is responsible for some of the Fe isotopic fractionation documented in felsic rocks and in particular in pegmatites. However, some granites with high δ56Fe values have unfractionated δ66Zn values and were presumably poor in fluids (e.g., A-type). For these samples, iron isotopic fractionation during magma differentiation is a viable interpretation. Equilibrium Fe isotopic fractionation factors between silicic melts and minerals remain to be characterized to quantitatively assess the role of fractional crystallization on iron isotopes in granitoids.