Iron Isotope Research Articles

How Homo-sapiens began our journeys on the Earth?

We provide a “reader digest” version about the life forms evolved on the Earth and wish to emigrant to the other planet. E.g. Moon, Mars. First of all, the enormous gravitational force attracted two huge massive black holes (because photons could not be escaped) into a big bang collision circa 13.8 billion years (estimated by the background radiation 3oK). It has produced the spinal shape Milky Way (due to the conservation of angular momentum). The Milky Way is filled with stars and planets, according to 2020 Nobel Prizes in Physics by Roger Penrose (Oxford) and Andrea Ghez(UCLA), as well as Reinhard Genzel (Max-Planck) based on the NSF NASA supported Laser Interference Gravitationwave Observation (LIGO) experiments (operated by MIT & Caltech). We wish to answer how we began our life journeys on the Earth. Burning hydrogen’s became the water on almost all the planets. The Sun fused about 13 helium atoms to the heavy element irons and ejected out and captured by the bigger and closer Earth than the Mars. Then the Earth core fission some iron isotopes generated spinning current produced kilo-Tesla magnetic field which has warded off the constant bombardment of solar flares burning off water from the Earth. The water interacted with other chemical element Nitrogen and Carbon to build about 20 amino acids to proteins for regenerative beings. The reproduction is made of billions twisted pairs and spooling winding together into DNA genes in each cell with dozen co-evolved partners Mitochondria with its own DNA into reproductive life.

Fluid-rock reactions of the Triassic Taiyangshan porphyry Cu-Mo deposit (West Qinling, China) constrained by QEMSCAN and iron isotope

The multiphase hydrothermal superposition phenomena on porphyry deposits, the mineral complexity and characteristics of the alteration-associated assemblages limit a further determination for the magmatic-hydrothermal evolution in porphyry deposits. The Taiyangshan porphyry Cu-Mo deposit in the northern margin of the Triassic West Qinling Orogenic Belt exhibits a multi-stage, alteration-related quartz sulfide veins that recorded element migration processes during fluid-rock reactions. In this study, we investigated hydrothermal veins in the Taiyangshan deposit focusing on vein compositions and structures as well as the evolution of ore formation, using quantitative evaluation of minerals by scanning electron microscopy (QEMSCAN) and iron isotope analyses. The formation of the early K-feldspar-biotite-quartz-magnetite-apatite veins is closely associated with the early potassic alteration, and during the fluid-rock reactions, Si, S, Fe, and K migrated in, while Mg, Ca and Na migrated out. K-feldspar-chlorite-pyrite-chalcopyrite-quartz veins correlated to the propylitic alteration, dominantly caused the migration of Si, Fe, S, Ca Mg, Al and K. Quartz-sericite-pyrite veins corresponding to the phyllic alteration processes that occurred in a relatively late stage, during the fluid-rock reactions of which, Si, Fe, S, and K migrated into the system. The δ56Fe whole-rock values of altered porphyries range from 0.08‰ to 0.31‰, and δ56Fe values of pyrite from quartz veins range from 0.30‰ to 0.57‰. Iron isotope compositions of both pyrites of the ore-bearing wall rocks and the quartz-sulfide veins of the Taiyangshan Cu-Mo deposit are generally uniform, which indicate the same source origin between the ore-bearing porphyry and the iron isotope compositions of the metal sulfide in the quartz veins, and additionally highlight that the ore-forming source is closely related to the ore-bearing porphyry. Magnetite precipitated in the early stage of potassic alteration, resulting in the enrichment of the light Fe isotope in the early fluids. Crystallization and precipitation of pyrite mainly occurred during processes of propylitic and phyllic alteration, leading to an absorption of the light Fe isotope, and elsewhere, an enrichment of the heavy Fe isotope in the fluids. During the fluid-rock reactions of propylitic and phyllic alteration, a large amount of S migrated into the veins, thereby promoting the fractionation of Fe isotope. Moreover, the development of the ore-forming fluids enriched with heavy Fe isotope from early potassic- to late phyllic alteration, are indicative of isotopic progressions from the early lithostatic pressure to the late hydrostatic pressure. Our research on the Taiyangshan Cu-Mo porphyry deposit helps to explain the evolutionary processes of the magmatic–hydrothermal system, and improves our understanding of the porphyry metallogenic evolution model.

Competing effects of spreading rate, crystal fractionation and source variability on Fe isotope systematics in mid-ocean ridge lavas

Two-thirds of the Earth is covered by mid-ocean ridge basalts, which form along a network of divergent plate margins. Basalts along these margins display a chemical diversity, which is consequent to a complex interplay of partial mantle melting in the upper mantle and magmatic differentiation processes in lower crustal levels. Igneous differentiation (crystal fractionation, partial melting) and source heterogeneity, in general, are key drivers creating variable chemistry in mid-ocean ridge basalts. This variability is reflected in iron isotope systematics (expressed as δ57Fe), showing a total range of 0.2 ‰ from δ57Fe = + 0.05 to + 0.25 ‰. Respective contributions of source heterogeneity and magma differentiation leading to this diversity, however, remain elusive. This study investigates the iron isotope systematics in basalts from the ultraslow spreading Gakkel Ridge in the Arctic Ocean and compares them to existing data from the fast spreading East Pacific Rise ridge. Results indicate that Gakkel lavas are driven to heavier iron isotope compositions through partial melting processes, whereas effects of igneous differentiation are minor. This is in stark contrast to fast spreading ridges showing reversed effects of near negligible partial melting effects followed by large isotope fractionation along the liquid line of descent. Gakkel lavas further reveal mantle heterogeneity that is superimposed on the igneous differentiation effects, showing that upper mantle Fe isotope heterogeneity can be transmitted into erupting basalts in the absence of homogenisation processes in sub-oceanic magma chambers.

Iron Isotopes and Trace Element Compositions of Magnetite from the Submarine Volcanic-Hosted Iron Deposits in East Tianshan, NW China: New Insights into the Mineralization Processes

The Aqishan-Yamansu metallogenic belt (AYMB) in East Tianshan hosts abundant submarine volcanic-hosted iron deposits. Although there is agreement with the magmatic source of the ore-forming materials and the role of hydrothermal replacement in iron ore formation, the mineralization processes of these iron deposits remain uncertain. Three ore types are identified on the basis of the geological occurrences of minerals and the sequence of mineral in ores. The type I ores are characterized by magnetite, diopside, amphibole with a few pyrite, and chalcopyrite. The type II ores are mainly composed of magnetite, garnet, chlorite with a few pyrite, while the type III ores are mainly composed of magnetite, quartz, calcite with a few pyrite. In order to constrain the mineralization processes of these ore types, we performed iron isotopes and trace element compositions of magnetite from three typical iron deposits (Yamansu, Duotoushan and Luotuofeng). Trace element and Fe isotope investigations of the three ore types reveal two major groups. The group I consists of analyses of the type I and II ores, with both showing a narrow range of positive δ56Fe values (+0.08‰ to +0.22‰ for type I ores and +0.15‰ to +0.22‰ for type II ores) and plotting in the range of the ortho-magmatic field. In contrast, the group 2 is composed merely of the type III ores, showing a wider range of negative δ56Fe values (-0.49‰ to -0.01‰), which is similar to the features of Fe-skarn magnetite. As shown in the binary diagrams of magnetite trace elements and a fractionation of the Fe isotopes, different ore types were likely produced during gradually changing ore-forming stages from magmatic to hydrothermal. Collectively, the submarine volcanic-hosted iron deposits in the East Tianshan are likely the results of a continuous magmatic-hydrothermal mineralization process.

Three-dimensional Supernova Models Provide New Insights into the Origins of Stardust

Abstract We present the isotope yields of two post-explosion, three-dimensional 15 core-collapse supernova models, 15S and 15A, and compare them to the carbon, nitrogen, silicon, aluminum, sulfur, calcium, titanium, iron, and nickel isotopic compositions of SiC stardust. We find that these core-collapse supernova models predict similar carbon and nitrogen compositions to SiC X grains and grains with 12C/13C < 20 and 14N/15N < 60, which we will hereafter refer to as SiC ‘D’ grains. Material from the interior of a 15 explosion reaches high enough temperatures shortly after core collapse to produce the large enrichments of 13C and 15N necessary to replicate the compositions of SiC D grains. The innermost ejecta in a core-collapse supernova is operating in the neutrino-driven regime and undergoes fast proton capture after being heated by the supernova shockwave. Both 3D models predict 0.3 Al/27Al < 1.5, comparable to the ratios seen in SiC X, C, and D grains. Models 15S and 15A, in general, predict very large anomalies in calcium isotopes but do compare qualitatively with the SiC X grain measurements that show 44Ca and 43Ca excesses. The titanium isotopic compositions of SiC X grains are well reproduced. The models predict 57Fe excesses and depletions that are observed in SiC X grains, and in addition predict accurately the 60Ni/58Ni, 61Ni/58Ni, and 62Ni/58Ni ratios in SiC X grains, as a result of fast neutron captures initiated by the propagation of the supernova shockwave. Finally, symmetry has a noticeable effect on the production of silicon, sulfur, and iron isotopes in the SN ejecta.

Energy deficit increases hepcidin and exacerbates declines in dietary iron absorption following strenuous physical activity: a randomized-controlled cross-over trial

Strenuous physical activity promotes inflammation and depletes muscle glycogen, which may increase the iron regulatory hormone hepcidin. Hepcidin reduces dietary iron absorption and may contribute to declines in iron status frequently observed following strenuous physical activity. To determine the effects of strenuous physical activity on hepcidin and dietary iron absorption and whether energy deficit compared with energy balance modifies those effects. This was a randomized, cross-over, controlled-feeding trial in healthy male subjects (n=10, mean±SD age: 22.4±5.4 y, weight: 87.3±10.9 kg) with sufficient iron status (serum ferritin 77.0±36.7 ng/mL). Rest measurements were collected before participants began a 72-h simulated sustained military operation (SUSOPS), designed to elicit high energy expenditure, glycogen depletion, and inflammation, followed by a 7-d recovery period. Two 72-h SUSOPS trials were performed where participants were randomly assigned to consume either energy matched (±10%) to their individual estimated total daily energy expenditure (BAL) or energy at 45% of total daily energy expenditure to induce energy deficit (DEF). On the rest day and at the completion of BAL and DEF, participants consumed a beverage containing 3.8 mg of a stable iron isotope, and plasma isotope appearance was measured over 6 h. Muscle glycogen declined during DEF and was preserved during BAL (-188±179 mmol/kg, P-adjusted<0.01). Despite similar increases in interleukin-6, plasma hepcidin increased during DEF but not BAL, such that hepcidin was 108% greater during DEF compared with BAL (7.8±12.2 ng/mL, P-adjusted<0.0001). Peak plasma isotope appearance at 120 min was 74% lower with DEF (59±38% change from 0 min) and 49% lower with BAL (117±81%) compared with rest (230±97%, P-adjusted<0.01 for all comparisons). Strenuous physical activity decreases dietary iron absorption compared with rest. Energy deficit exacerbates both the hepcidin response to physical activity and declines in dietary iron absorption compared with energy balance. This trial was registered at clinicaltrials.gov as NCT03524690.

Does ultrafiltration kinetics bias iron isotope compositions?

Iron (Fe) isotopes are now recognized as useful tracers of Fe sources and biogeochemical processes in natural environments but many uncertainties remain regarding the mechanisms that control their isotopic fractionation. Ultrafiltration techniques applied to separate Fe species could potentially bias Fe isotopic compositions. Here, we investigated frontal centrifugal ultrafiltration. We have set up time-ultrafiltration experiments at low and high Fe concentrations both with and without organic matter (OM) at pH values of 1 and 6.5. The ultrafiltration impact was studied by monitoring the Fe isotope composition in the <30 kDa ultrafiltrates relative to the ultrafiltration time. No Fe isotopes bias resulted from the ultrafiltration technique regardless the Fe and OM concentrations and speciation. This work, therefore, validates the use of the frontal centrifugal ultrafiltration technique to study the signature of Fe isotopes in environmental samples composed of various Fe species sizes such as colloids, nanoparticles, clusters or soluble complexes.

More than redox, biological organic ligands control iron isotope fractionation in the riparian wetland

Although redox reactions are recognized to fractionate iron (Fe) isotopes, the dominant mechanisms controlling the Fe isotope fractionation and notably the role of organic matter (OM) are still debated. Here, we demonstrate how binding to organic ligands governs Fe isotope fractionation beyond that arising from redox reactions. The reductive biodissolution of soil Fe(III) enriched the solution in light Fe isotopes, whereas, with the extended reduction, the preferential binding of heavy Fe isotopes to large biological organic ligands enriched the solution in heavy Fe isotopes. Under oxic conditions, the aggregation/sedimentation of Fe(III) nano-oxides with OM resulted in an initial enrichment of the solution in light Fe isotopes. However, heavy Fe isotopes progressively dominate the solution composition in response to their binding with large biologically-derived organic ligands. Confronted with field data, these results demonstrate that Fe isotope systematics in wetlands are controlled by the OM flux, masking Fe isotope fractionation arising from redox reactions. This work sheds light on an overseen aspect of Fe isotopic fractionation and calls for a reevaluation of the parameters controlling the Fe isotopes fractionation to clarify the interpretation of the Fe isotopic signature.

Impact of deforestation on soil iron chemistry and isotope signatures in Amazonia

We examined the consequences of soil erosion processes following deforestation and long-term pasture establishment for soil chemical and physical properties and Fe isotope compositions within two distinct areas in the Eastern and Central parts of Amazonia (near Rio Capim, Para, Brazil and Lake Balbina/Rio Uatuma, Amazonas, Brazil).For each area studied, soils selected under forest cover and pasture or after recent slash-and-burn practices were investigated. In both forest ecosystems studied, pedogenesis along slopes reflects the evolution of lateritic crust bearing soils (Ferralsol) into iron depleted soils after leaching (Acrisol) and redox processes (Gleysol). Measurements performed by plasma source mass spectrometry show a large range of iron isotope signature within the soil profiles studied at the bottom of the slopes (i.e. foot slope and/or valley soils), under both forest and pasture. Iron isotopic signature in foot slope soils under forest cover (δ57FeIRMM-14 ~ +0.2 to +0.6‰) and pasture (δ57FeIRMM-14 ~ +0.3‰) are significantly heavier than both the continental crust baseline and the reference ferralitic soils from the top of the hill (δ57FeIRMM-14 ~ +0.1‰). This enrichment in heavy isotopes is attributed to the preferential mobilisation and loss of light iron during pedogenesis that involves redox processes in areas periodically flooded at the foot slope and valley soils. Under forest, light iron depletion (where ~90% of the iron was leached in the first metre of the soil) has greater influence on the soil isotopes signature, particularly in foot slope sand-rich soils close to the river system with a remaining Fe having δ57Fe IRMM-14 ~ +0.6‰. Under pasture where soils experienced erosion processes, iron depletion in foot slope and riverside soils is less important (where only a little more than half of the iron was leached in the first metre of the soil) and the resulting δ57FeIRMM-14 ~ +0.4‰ suggests an input of light iron isotopes via colluvic material deposition. This difference indicates that geomorphological changes due to erosion processes following deforestation (i.e. colluvic processes) lead to an “isotopic rejuvenation” of the soils in the valley, mostly apparent within the riverside soils.For comparison, we investigated isotopic changes in a recently deforested small watershed, near Lake Balbina, Central Amazonia, focusing on riverside soils. Results confirm that the isotopic rejuvenation effect appears within a few months following the first stage of deforestation as a consequence of erosion processes following slash-and-burn practices. Erosion can remove isotopically lighter (i.e. close to the continental crust value of ~0.1‰ in δ57Fe) iron bearing soil material from the top of the hill. When such colluvial soil material accumulates in the bottom of the hills on soils that were initially depleted in light iron isotopes, again due to podzolisation as described in the previous site, it induces an “isotopic rejuvenation” (tending again towards a lighter, continental crust-like δ57Fe signature) of the foot slope and riverside soils, besides changes in landscape morphology, water drainage and soil functioning (i.e. hydromorphic processes). Hence, this study illustrates that Fe isotopes can be used to identify erosion within a deforestation context through “isotope rejuvenation”, even when soil textures make it challenging to unravel.

Iron and Carbon Isotope Constraints on the Formation Pathway of Iron-Rich Carbonates within the Dagushan Iron Formation, North China Craton

Banded iron formations (BIFs) are enigmatic chemical sedimentary rocks that chronicle the geochemical and microbial cycling of iron and carbon in the Precambrian. However, the formation pathways of Fe carbonate, namely siderite, remain disputed. Here, we provide photomicrographs, Fe, C and O isotope of siderite, and organic C isotope of the whole rock from the ~2.52 Ga Dagushan BIF in the Anshan area, China, to discuss the origin of siderite. There are small magnetite grains that occur as inclusions within siderite, suggesting a diagenetic origin of the siderite. Moreover, the siderites have a wide range of iron isotope compositions (δ56FeSd) from −0.180‰ to +0.463‰, and a relatively negative C isotope composition (δ13CSd = −6.20‰ to −1.57‰). These results are compatible with the reduction of an Fe(III)-oxyhydroxide precursor to dissolved Fe(II) through microbial dissimilatory iron reduction (DIR) during early diagenesis. Partial reduction of the precursor and possible mixing with seawater Fe(II) could explain the presence of siderite with negative δ56Fe, while sustained reaction of residual Fe(III)-oxyhydroxide could have produced siderite with positive δ56Fe values. Bicarbonate derived from both DIR and seawater may have provided a C source for siderite formation. Our results suggest that microbial respiration played an important role in the formation of siderite in the late Archean Dagushan BIF.

Iron and sulfur isotopes of sulfides from the Wocan hydrothermal field on the Carlsberg Ridge, Indian Ocean

The basalt-hosted Wocan hydrothermal field (WHF) was identified in 2013 during Chinese Dayang 28th cruise, which is located on the slow-spreading Carlsberg Ridge, northwest Indian Ocean. Few investigation has been carried out on the hydrothermal activities and associated sulfide deposit in this area. Herein, we report Fe and S isotope compositions of sulfide minerals including chalcopyrite, bornite, pyrite and sphalerite collected from the WHF. The results showed that all sulfide minerals display small δ34S variations (2.44‰ to 5.37‰, with an average of 4.00‰), and a wide δ56Fe range (−2.05‰ to 0.10‰, with an average of −0.92‰). Sulfur and iron isotopes in paired pyrite and chalcopyrite minerals reveal that it did not reach the equilibrium fractionation during pyrite precipitation, and support that the FeS precipitates first during the pyrite formation. The δ56Fe values of chalcopyrite and concurrent bornite are characterized by a well-defined negative correlation, which may be related to the repeated dissolution-reprecipitation of these copper-bearing sulfides under Fe-limited conditions. Most pyrites from the WHF demonstrate a positive correlation between δ56Fe and δ34S values, in accord with those from other hydrothermal fields, which can be explained by the temperature gradient and similar degrees of isotope exchange in the stable hydrothermal system. Conversely, the δ56Fe and δ34S values of chalcopyrite exhibit a slightly negative correlation, in which the temperature gradient can explain the negative correlation, but cannot cover the wide ranges of δ56Fe and δ34S values. More work on fractionation parameters and chalcopyrite formation mechanisms is still needed. In summary, the coupling of Fe and S isotopes is a useful tool in helping to delineate processes of sulfide mineralization in hydrothermal systems

Iron isotopic compositions of combustion source particles and mineral dust

Iron,one of the essential micronutrients for life,would largely promote oceanic primary productivity. Atmospheric deposition has been recognized as the dominant source of bioavailable iron in the open ocean;however,the relative contribution of combustion aerosol and mineral dust to bioavailable iron in the ocean remains poorly understood. The development of iron isotope techniques provides a new way for tracing iron sources. The application of iron isotope technique in atmospheric and oceanic sciences is still limited,and iron isotopic compositions of aerosols from various sources are not well understood. In this study,we selected one Chinese coal fly ash,two American coal fly ashes,one European city waste fly ash and three mineral dust samples from different regions (Arizona test dust from America,Luochuan Loess from China,and Xinjiang dust from China) and measured their iron contents and iron isotopic compositions. The maximum mass fraction of iron in coal fly ash was measured to be ~10%,significantly higher than those for city waste fly ash and mineral dust (both in the range of 2% to 4%). The δ56Fe values were determined to be 0.05‰-0.75‰ for the four fly ash samples and -0.05‰-0.21‰ for three mineral dust samples,respectively. Compared with mineral dust,combustion source particles showed heavier iron isotopic compositions,probably attributed to large variations in physicochemical properties of fuels and fly ashes.

New potential pyrrhotite and pentlandite reference materials for sulfur and iron isotope microanalysis

In this study, natural pyrrhotite and pentlandite were investigated as two new potential reference materials for both sulfur and iron isotopes by micro-beam methods.

Anoxic continental surface weathering recorded by the 2.95 Ga Denny Dalton Paleosol (Pongola Supergroup, South Africa)

Iron mobilization during continental weathering was pervasive before the Great Oxidation Event (GOE) that started at around 2.43 billion years (Ga) ago, due to the soluble nature of reduced iron. However, various geochemical proxies indicate transient oxygenation during deposition of the Mesoarchean (∼2.95 Ga) Pongola Supergroup, South Africa, which suggests that continental weathering could have also occurred under transiently oxic conditions before the GOE. We analyzed trace elemental and Fe, Ti, and Cr isotopic compositions of the ca. 2.95 Ga Denny Dalton paleosol in the Pongola Supergroup to better understand continental weathering and redox conditions in the ancient critical zone, and the nature of geochemical fluxes from the continents to the oceans and marine sediments. Iron isotope systematics are consistent with a model where Fe was released during intense leaching from the paleosol to concentrate in Fe-rich groundwaters in the deeper part of the soil horizon. We show for the first time that Fe isotopic fractionation during Mesoarchean continental weathering was limited, and Fe enrichments and depletions are coupled with those of divalent transition metals, Co, Ni, and particularly Zn. This suggests that Fe redox cycling was not involved in paleosol formation, and Fe2+ was mobilized under anoxic conditions. Chromium isotopes are also unfractionated relative to the parent igneous rock in this paleosol, which precludes removal of isotopically heavy Cr6+ and thus supports anoxic continental weathering. We show that previously reported Cr isotopic fractionation in another Denny Dalton paleosol profile does not follow a Cr6+ leaching trend, but instead scales with Cr enrichment and may reveal Cr enrichment from post-burial fluids. Thus, there is no clear evidence for an oxidative continental weathering during deposition of the Pongola Supergroup. Titanium isotopes are not significantly fractionated in the paleosol, suggesting that continental weathering and erosion in the Archean did not fractionate Ti isotopes. Similarly, Ni/Co and Th/Sc ratios are reasonably conserved, which validates their use as a robust proxy for upper continental crust composition in shales, whereas La/Sc, Cr/Zn and Cr/U ratios are highly variable relative to the provenance composition, which suggests that caution should be used when applying these ratios in shale studies of the ancient upper continental crust composition.

Iron and zinc stable isotope evidence for open-system high-pressure dehydration of antigorite serpentinite in subduction zones

Subducted serpentinites have the potential to control the exchange of volatile and redox sensitive elements (e.g., Fe, S, C, N) between the slab, the mantle wedge and the deep mantle. Here we examine the mobility of iron and zinc in serpentinite-derived fluids by using their stable isotopes (δ56Fe and δ66Zn) in high-pressure subducted meta-serpentinites from the Cerro del Almirez massif (Spain). This massif preserves a metamorphic front between antigorite (Atg-serpentinite) and antigorite-olivine-orthopyroxene (transitional lithologies) -bearing serpentinites, and chlorite-bearing harzburgite (Chl-harzburgite), displaying granofels, spinifex and fine-grained recrystallized textures. Those rocks were formed at eclogite facies conditions (1.6–1.9 GPa and 680–710 °C). The mean δ56Fe of all the Cerro del Almirez meta-serpentinites (+0.05 ± 0.01‰) is identical within an error to that of primitive mantle (+0.03 ± 0.03‰). A positive correlation between δ56Fe and indices of peridotite protolith fertility (e.g., Al2O3/SiO2) suggests that the δ56Fe values of Cerro del Almirez samples predominantly reflect protolith compositional variations, likely produced by prior episodes of melt extraction. In contrast, the Zn concentrations ([Zn] = 34–67 ppm) and isotope signatures (δ66Zn = +0.18 – +0.55‰) of the Cerro del Almirez samples show a broad range of values, distinct to those of the primitive mantle ([Zn] = 54 ppm; δ66Zn = +0.16 ± 0.06‰). The Atg-serpentinites ([Zn] = 34–46 ppm; δ66Zn = +0.23 ± 0.06‰) display similar [Zn] and δ66Zn values to those of slab serpentinites from other high-pressure meta-ophiolites. Both [Zn] and δ66Zn increase in transitional lithologies ([Zn] = 45–67 ppm; δ66Zn = +0.30 ± 0.06‰) and Chl-harzburgites with granofels ([Zn] = 38–59 ppm; δ66Zn = +0.33 ± 0.04‰) or spinifex ([Zn] = 48–66 ppm; δ66Zn = +0.43 ± 0.09‰) textures. Importantly, Cerro del Almirez transitional lithologies and Chl-harzburgites display abnormally high [Zn] relative to abyssal peridotites and serpentinites (29–45 ppm) and a positive correlation exists between [Zn] and δ66Zn. This correlation is interpreted to reflect the mobilization of Zn by subduction zone fluids at high pressures and temperatures coupled with significant Zn stable isotope fractionation. An increase in [Zn] and δ66Zn from Atg-serpentinite to Chl-harzburgite is associated with an increase in U/Yb, Sr/Y, Ba/Ce and Rb/Ce, suggesting that both [Zn] and δ66Zn record the interaction of the transitional lithologies and the Chl-harzburgites with fluids that had equilibrated with metasedimentary rocks. Quantitative models show that metasediment derived fluids can have isotopically heavy Zn as a consequence of sediment carbonate dissolution and subsequent Zn complexation with carbonate species in the released fluids (e.g., [ZnHCO3(H2O)5+] or [ZnCO3(H2O)3]). Our models further demonstrate that Zn complexation with reduced carbon species cannot produce fluids with heavy δ66Zn signature and hence explain the δ66Zn variations observed in the Chl-harzburgites. The most straightforward explanation for the heavy δ66Zn of the Cerro del Almirez samples is thus serpentinite dehydration accompanied by the open system infiltration of the massif by oxidized, carbonate-rich sediment-derived fluids released during prograde subduction-related metamorphism.

High-spatial-resolution measurements of iron isotopes in pyrites by secondary ion mass spectrometry using the new Hyperion-II radio-frequency plasma source.

Iron isotopic signatures in pyrites are considered as a good proxy for reconstructing paleoenvironmental and local redox conditions. However, the investigation of micro-pyrites less than 20 μm in size has been limited by the available analytical techniques. The development of a new brighter radio-frequency plasma ion source (Hyperion-II source) enhances the spatial resolution by increasing the beam density 10 times compared with the Duoplasmatron source. Here we present high-spatial-resolution measurements of iron isotopes in pyrites using a 3 nA-3 μm primary 16 O- beam on two Cameca IMS 1280-HR2 ion microprobe instruments equipped with Hyperion sources at CRPG-IPNT (France) and at SwissSIMS (Switzerland). We tested analytical effects, such as topography and crystal orientation, that could induce analytical biases perceptible through variations of the instrumental mass fractionation (IMF). The δ56 Fe reproducibility for the Balmat pyrite standard is ±0.25‰ (2 standard deviations) and the typical individual internal error is ±0.10‰ (2 standard errors). The sensitivity on 56 Fe+ was 1.2 × 107 cps/nA/ppm or better. Tests on Balmat pyrites revealed that neither the crystal orientation nor channeling effects seem to significantly influence the IMF. Different pyrite standards (Balmat and SpainCR) were used to test the accuracy of the measurements. Indium mounts must be carefully prepared with a sample topography less than 2 μm, which was checked using an interferometric microscope. Such a topography is negligible for introducing change in the IMF. This new source increases the spatial resolution while maintaining the high precision of analyses and the overall stability of the measurements compared with the previous Duoplasmatron source. A reliable method was developed for performing accurate and high-resolution measurements of micrometric pyrites. The investigation of sedimentary micro-pyrites will improve our understanding of the processes and environmental conditions during pyrite precipitation, including the contribution of primary (microbial activities or abiotic reactions) and secondary (diagenesis and/or hydrothermal fluid circulation) signatures.

Iron force constants of bridgmanite at high pressure: Implications for iron isotope fractionation in the deep mantle

The isotopic compositions of iron in major mantle minerals may record chemical exchange between deep-Earth reservoirs as a result of early differentiation and ongoing plate tectonics processes. Bridgmanite (Bdg), the most abundant mineral in the Earth’s lower mantle, can incorporate not only Al but also Fe with different oxidation states and spin states, which in turn can influence the distribution of Fe isotopes between Bdg and ferropericlase (Fp) and between the lower mantle and the core. In this study, we combined first-principles calculations with high-pressure nuclear resonant inelastic X-ray scattering measurements to evaluate the effects of Fe site occupancy, valence, and spin states at lower-mantle conditions on the reduced Fe partition function ratio (β-factor) of Bdg. Our results show that the spin transition of octahedral-site (B-site) Fe3+ in Bdg under mid-lower-mantle conditions generates a +0.09‰ increase in its β-factor, which is the most significant effect compared to Fe site occupancy and valence. Fe2+-bearing Bdg varieties have smaller β-factors relative to Fe3+-bearing varieties, especially those containing B-site Fe3+. Our models suggest that Fe isotopic fractionation between Bdg and Fp is only significant in the lowermost mantle due to the occurrence of low-spin Fe2+ in Fp. Assuming early segregation of an iron core from a deep magma ocean, we find that neither core formation nor magma ocean crystallization would have resulted in resolvable Fe isotope fractionation. In contrast, Fe isotopic fractionation between low-spin Fe3+-bearing Bdg/Fe2+-bearing Fp and metallic iron at the core-mantle boundary may have enriched the lowermost mantle in heavy Fe isotopes by up to +0.20‰.

Iron Absorption is Greater from Apo-Lactoferrin and is Similar Between Holo-Lactoferrin and Ferrous Sulfate: Stable Iron Isotope Studies in Kenyan Infants

Whether lactoferrin (Lf) binds iron to facilitate its absorption or to sequester iron from potential enteropathogens remains uncertain. Bovine Lf is added to many infant formulas, but previous studies in infants reported that Lf had no effect on or inhibited iron absorption. The effects of the apo (iron-free) or the holo (iron-loaded) forms of Lf on iron absorption are unclear. Our objective was to compare iron absorption from a maize-based porridge containing: 1) labeled ferrous sulfate (FeSO4) alone; 2) labeled FeSO4 given with bovine apo-Lf; and 3) intrinsically labeled bovine holo-Lf. In a crossover study, we measured iron absorption in Kenyan infants (n=25; mean±SD age 4.2±0.9 months; mean±SD hemoglobin 109±11g/L) from maize-based test meals containing: 1) 1.5mg of iron as 54Fe-labeled FeSO4; 2) 1.42mg of iron as 58Fe-labeled FeSO4, given with 1.41g apo-Lf (containing 0.08mg iron); and 3) 1.41g holo-Lf carrying 1.5mg iron as 57Fe. The iron saturation levels of apo- and holo-Lf were 0.56% and 47.26%, respectively primary outcome was fractional iron absorption (FIA), assessed by erythrocyte incorporation of isotopic labels. The FIA from the meal containing apo-Lf+FeSO4 (geometric mean, 9.8%; -SD and +SD, 5.4% and 17.5%) was higher than from the meals containing FeSO4 (geometric mean, 6.3%; -SD and +SD, 3.2% and 12.6%; P=0.002) or holo-Lf (geometric mean, 5.0%; -SD and +SD, 2.8% and 8.9%; P <0.0001). There was no significant difference in FIA when comparing the meals containing holo-Lf versus FeSO4 alone (P=0.24). The amount of iron absorbed from holo-Lf was comparable to that of FeSO4, and the addition of apo-Lf to a test meal containing FeSO4 significantly increased (+56%) iron absorption. These findings suggest that Lf facilitates iron absorption in young infants. Because Lf binds iron with high affinity, it could be a safe way to provide iron to infants in low-income countries, where iron fortificants can adversely affect the gut microbiome and cause diarrhea. This study was registered at clinicaltrials.gov as NCT03617575.

Exceptional sulfur and iron isotope enrichment in millimetre-sized, early Palaeozoic animal burrows

Pyrite-δ34S and -δ56Fe isotopes represent highly sensitive diagnostic paleoenvironmental proxies that express high variability at the bed (< 10 mm) scale that has so far defied explanation by a single formative process. This study reveals for the first time the paleoenvironmental context of exceptionally enriched pyrite-δ34S and -δ56Fe in bioturbated, storm-reworked mudstones of an early Ordovician storm-dominated delta (Tremadocian Beach Formation, Bell Island Group, Newfoundland). Very few studies provide insight into the low-temperature sulfur and iron cycling from bioturbated muddy settings for time periods prior to the evolution of deep soil horizons on land. Secondary ion mass spectroscopy (SIMS) analyses performed on Beach Formation muddy storm event beds reveal spatially distinct δ34S and δ56Fe values in: (a) tubular biogenic structures and trails (δ34S ~ +40‰; δ56Fe ~ −0.5‰), (b) silt-filled Planolites burrows (δ34S ~ +40‰; δ56Fe ~ +0.5 to + 2.1‰), and (c) non-bioturbated mudstone (δ34S ~ +35‰; δ56Fe ~ +0.5‰). δ34S values of well above + 40.0‰ indicate at least some pyrite precipitation in the presence of a 34S-depleted pore water sulfide reservoir, via closed system (Raleigh-type) fractionation. The preferential enrichment of 56Fe in Planolites burrows is best explained via microbially-driven liberation of Fe(II) from solid iron parent phases and precipitation from a depleted 54Fe dissolved Fe(II) reservoir. Rigorous sedimentological analysis represents a gateway to critically test the paleoenvironmental models describing the formation of a wide range of mudstones and elucidates the origins of variability in the global stable S and Fe isotope record.

Problem of Iron Isotope Composition of the Earth and Moon. Data on δ57Fe of Luna 16, Luna 20, and Luna 24 Lunar Soil Samples (Report on the XXII Symposium on the Geochemistry of Stable Isotopes, Moscow, October 29–31, 2019)

The model of the formation of the Earth–Moon system during the compression and fragmentation of a gas–dust cloud (Galimov, 2011; Galimov and Krivtsov, 2012) suggests an unusual mechanism for the formation of the Earth’s core. In particular, the model predicts that iron in the Earth’s core should be enriched in the light isotope, and the Earth’s mantle should be, conversely, enriched in the heavy isotope compared to the primary iron (of chondrites). The alternative (megaimpact) model does not allow for this phenomenon. This problem could be solved by comparing the iron isotope composition of the Earth’s and Moon’s mantles. The best representation of the iron isotope composition of the lunar mantle (δ57Fe) is given by the Fe isotope composition of lunar basalts with very low titanium content (VLT), just as the best representation of the isotope composition of iron in the Earth’s mantle is given by the δ57Fe of the Earth’s mid-oceanic ridge basalts (MORB). VLT basalts are relatively scarce on the lunar surface, unlike high-titanium basalts, which fill lunar lowlands. Their iron isotope composition has not yet been measured. We were the first to analyze the iron isotope composition of very low-titanium lunar basalts (VLT) in material delivered by the Luna 24 space mission. Our data indicate that the δ57Fe of Earth’s mantle is higher than the δ57Fe of the bulk silicate Moon, which means (with a high degree of probability) that the Earth’s core is enriched in the light iron isotope. This, in turn, is in good agreement with the model of formation of the Earth–Moon system by the compression and fragmentation of the gas–dust cloud.