Stable Fe Isotope Research Articles

Iron cycling and isotopic fractionation in a ferruginous, seasonally ice-covered lake

Ferruginous conditions, defined by anoxia and abundant dissolved ferrous iron (Fe2+aq), dominated the Precambrian oceans but are essentially non-existent in a modern, oxygenated world. Ferruginous meromictic lakes represent natural laboratories to ground truth our understanding of the stable Fe isotope proxy, which has been used extensively in interpreting the origins of Fe-rich sedimentary rocks like iron formations (IFs) and the interactions of early life with high-Fe2+aq conditions. Here we report comprehensive geochemical and Fe isotopic analyses of samples collected in May and August 2022, and March 2023, from Deming Lake, Minnesota, a ferruginous meromictic lake that undergoes surface freezing in winter and never becomes euxinic. Through chemical and Fe isotopic analyses of different putative Fe sources to Deming Lake; including eolian input trapped in winter ice cover, nearby bogs, and regional groundwaters sampled at surface springs; we find that a groundwater source provides the best chemical and Fe isotopic match for Deming Lake and can support Fe2+aq-rich waters at depth that maintain a permanent chemocline at ∼12 m. The ice-free Deming Lake water column can be split into three layers dominated by distinct Fe cycling regimes. Layer (I) extends from the lake surface to the base of the oxycline at ∼6 m, and its Fe cycling is dominated by isotopically light Fe uptake into biomass, likely from stabilized dissolved Fe3+, with variable eolian lithogenic influences. Layer (II) extends between the oxycline and the chemocline at ∼12 m and is dominated by partial Fe2+aq oxidation on approach to the oxycline, with the formation of variably isotopically heavy Fe3+-bearing particles. Layer (III) underlies the chemocline and is defined by Fe2+ phosphate (vivianite) and carbonate saturation and precipitation under anoxic, Fe2+aq-rich conditions with little Fe isotopic fractionation. The ice-covered winter water column features more homogenous Fe chemistry above the chemocline, which we attribute to seasonal homogenization of Layers (I) and (II), with suppressed ferric particle formation. Authigenic Fe minerals with non-crustal (light) Fe isotopic compositions only appreciably accumulate in sediments in Deming Lake underlying the chemocline. All sediments deposited above 12 m appear crustal in their Fe isotopic, Mn/Fe, and Fe/Al ratios, likely revealing efficient reductive dissolution of Fe3+-bearing lake precipitates and remineralization of Fe-bearing biomass. We find limited fractionation of Fe isotopes in the ice-covered water column and suggest this provides evidence that substantial delivery of oxidants is required to generate highly fractionated Fe isotopic compositions in Sturtian Snowball era IFs. By comparing Fe isotopic and Mn/Fe fractionation trends in the different Deming Lake layers, we also suggest that correlations between these two parameters in giant early Paleoproterozoic IFs requires the simultaneous deposition of multiple authigenic phases on the ancient seafloor. Finally, high-precision triple Fe isotopic analyses of dissolved Fe impacted by extensive oxidation near the Deming Lake oxycline reveal that the slope of the mass fractionation law for natural, O2-mediated Fe2+aq oxidation is identical to those previously defined for both UV photo-oxidation, and for an array of highly fractionated Paleoproterozoic IFs.

Evidence for isotopically light Fe mobility under oxidising conditions in subduction zone fluids: A record of Monviso meta-serpentinites, Western Alps

The isotopically light Fe signature of arc magmas relative to mid-oceanic ridge basalts (MORB) is expected to be related to the redox state of their source. This implies a link between Fe mobility and redox variations across subduction zones. Here we address slab chemical variations during prograde metamorphism through a comprehensive geochemical study, including major, trace elements and Fe stable isotope (δ56Fe) analyses, of meta-serpentinites composing the eclogitic meta-ophiolite of the Monviso massif (Western Alps, Italy). These rocks partly preserve mantle related geochemical heterogeneities, as supported by negative correlations between fluid immobile elements (High Field Strong Elements) and LREE/HREE (Light – Heavy Rare Earth Elements) ratios. They are however characterized by large Cs enrichments relative to U or alkali elements suggesting that abyssal fluid mobile elements signature was overprinted by subduction related processes. Meta-serpentinites display large δ56Fe variations, from -0.20 ± 0.05 ‰ to +0.09 ± 0.03 ‰. Mineral separate analyses of olivine bearing veins show low Δ56Fe between olivine and magnetite (∼ 0.4 ‰), which according to Fe isotope thermometry correspond to high temperature equilibration, estimated between 530 and 550 °C, compatible with Monviso metamorphic climax (520–570 °C and 2.6–2.7 GPa). These results, in combination with geochemical modelling, confirm a reset of δ56Fe signature of abyssal serpentinites during prograde metamorphism in subduction zones. The bulk rock δ56Fe values of Monviso meta-serpentinites are negatively correlated with their Fe3+/∑Fe and As concentrations (a redox-sensitive and fluid mobile element). These correlations can be attributed to a metasomatism by external fluids derived from slab serpentinites during subduction. It also concords with the oxygen fugacity (fO2) record in meta-serpentinites, with meta-serpentinites equilibrated at high fO2 displaying the lowest δ56Fe values while samples equilibrated at low fO2 display mantle like δ56Fe signatures. These results highlight that oxidising conditions during serpentinite dehydration are likely to boost isotopically light Fe mobility in slab derived fluids.

Source and fate of atmospheric iron supplied to the subarctic North Pacific traced by stable iron isotope ratios

The availability of dissolved iron (Fe) limits primary production over some regions of the surface ocean, especially in regions such as the subarctic North Pacific. In this work, we use Fe stable isotope ratios (δ56Fe) in bulk and size-fractionated marine aerosol particles and dissolved Fe of surface seawater in the subarctic North Pacific on Japanese GEOTRACES cruise GP02 (Summer 2017) as a tracer to clarify the relative contribution of combustion and natural Fe in both marine aerosol particles and surface seawater. The bulk aerosols collected in the coastal regions of both East Asia and western North Pacific have total δ56Fe values that are as low as −0.5 ‰ when compared to crustal (+0.1 ‰), with both the water-soluble phase and the fine particles even more fractionated (as low as −1.9 and −2.8 ‰, respectively). The negative correlation between the aerosol δ56Fe signatures and the enrichment factors of Fe and other elements dominated by anthropogenic sources (e.g., lead and cadmium) in these coastal regions indicates the presence of Fe emitted from high-temperature combustion sources, such as coal combustion and metal smelting. In these regions, combustion Fe accounts for 4–13 and 13–45 % of the total and water-soluble aerosol Fe, respectively. The results demonstrate that soluble aerosol Fe sourced from combustion Fe can be equivalent to that sourced from natural dust Fe in these coastal regions. By contrast, the aerosol particles in pelagic regions were near crustal δ56Fe in all particle size fractions, indicating the dominance of natural Fe and little to no combustion Fe. The relationships among the fractional Fe solubility, major ion concentration, Fe species, and δ56Fe indicate that the presence of combustion Fe is the dominant reason for the solubility increase in the coastal regions and that the atmospheric processing of mineral dust during transport is more important in the pelagic regions. The dissolved Fe of the surface seawater at 10 m depth had a consistently higher δ56Fe by up to +1.5 ‰ than that of the simultaneously collected water-soluble aerosol Fe. The pattern of the elevated δ56Fe in the surface seawater corresponds to decreasing Fe concentrations and can be approximated by Rayleigh fractionation; we attribute these elevated surface δ56Fe values to the effect of biological uptake. New Fe fluxes from both the atmosphere and deeper depths are limited at least in summer compared with the biological uptake in the open ocean of the subarctic North Pacific.

Iron isotope evidence in continental intraplate basalts for mantle lithosphere imprint on heterogenous asthenospheric melts

Iron isotope studies on ocean island basalts (OIBs) and mid-ocean ridge basalts (MORBs) have disclosed the contribution of pyroxenite lithologies in the generation of basaltic magmas. Whether Fe isotopic compositions of continental intraplate basalts can be applied to trace lithological heterogeneity within the mantle source regions remains poorly investigated. To explore the systematics of stable Fe isotopes as a potential probe of lithological heterogeneity in the source of continental intraplate basalts, we present twenty-four Fe isotope data on a suite of well-characterized Cenozoic basalts from SE China. The samples show a large range of Fe isotope values (δ56Fe = +0.09‰ to +0.20‰), which correlate with SiO2, CaO/Al2O3, Ti/Eu, Hf/Hf*, Zr/Nb, Dy/Yb, La/Yb, Nb/Y, K/La, Sr/Ce, δ66Zn and estimated equilibrium pressures. The samples with the highest δ56Fe values represent early-stage low-silica basalts with moderately enriched Sr-Nd isotope ratios and high δ66Zn values, while the late-stage high-silica basalts display a broad δ56Fe decrease with increasing 87Sr/86Sr and with decreasing εNd and δ66Zn. We demonstrate that the heaviest Fe isotope signatures cannot be derived from a pure peridotite source and require a pyroxenite component in the source. Combined with other geochemical proxies, we show that the heaviest basalt compositions are consistent with low-degree melts produced by the adiabatic decompression of a carbonated pyroxenite-bearing asthenospheric mantle. Mixing of these hybrid melts with melt produced from in-situ melting of the subduction-modified sub-continental lithospheric mantle (SCLM) reproduces the Fe-isotope variability of the late-stage basalts. Our results demonstrate the significance of lithological heterogeneity in the mantle source of continental intraplate basalts and highlight the subsequent imprint of mantle lithosphere in the evolution of their Fe isotope compositions. Finally, this study exemplifies the potential of the Fe-Zn stable isotope pair for mantle geochemistry; coupled with traditional radiogenic isotopes and major and trace element concentrations, they formed an efficient tool to trace the nature and contribution of the mantle source components in the formation of intraplate basalts.

An amphibolitic source for “adakitic” I-type plutons in continental collision zones

Rocks with “adakitic” affinities are widespread in continental collision zones, recording important information about crustal thickening. Residual garnet during partial melting of the lower crust is traditionally considered to be responsible for heavy rare earth element and Y depletion, which is a key characteristic feature of these rocks. However, magmatic garnet is rarely observed in such adakitic igneous rocks and associated protolithic eclogite is also rarely reported. Instead, amphibole is a proposed abundant phase in lower arc crust. Whilst both garnet- and amphibole-rich assemblages can act as potential sources for intracrustal intermediate-silicic melts, their distinctive fractionation of fSm/Nd and fLu/Hf should, with time, lead to different Nd-Hf isotopic compositions in high Sr/Y rocks. Here we report whole-rock radiogenic Sr-Nd-Hf and stable Fe isotope compositions of well-characterized Oligocene to Miocene (33-14 Ma), post-collisional high-K adakitic intrusions from the Gangdese belt, South Tibet. The plutons have a low alumina saturation index and depleted Dy/Yb, pointing to negligible amounts of sediment contribution. They are characterized by variable initial 87Sr/86Sr ratios (0.7048 to 0.7078), mostly negative εNd (−4.9 to +0.3), positive εHf values (+1.5 to +8.3), and variable but heavy δ57Fe values ranging from +0.04 ± 0.08‰ to +0.35 ± 0.08‰. Modeling of Fe isotopes and fractionation factors of fSm/Nd and fLu/Hf indicate an amphibolite source. A Nd-Hf isotope correlation that is quasi-parallel to the mantle array can be best explained by the evolution of amphibolitic lower crust with a residence time of ca. 400 Myrs. Although these adakitic rocks have depleted, mantle-like Hf isotope compositions, they are part of an existing, older crustal foundation and thus represent a process of crustal reworking, instead of crustal growth. Therefore, proportions of mantle-derived materials that contributed to the Phanerozoic crustal growth based on Hf-in-zircon signatures alone may be overestimated. Combined mineral and whole-rock radiogenic and stable isotopes are required to address this issue in the future.

Tissue-variation of iron stable isotopes in marine fish coupled with speciation analysis using X-ray absorption fine structure

The Fe stable isotope ratio (δ56Fe) in tissues is a potential parameter for examining the Fe metabolism in marine fish. Although the effect of ferritin storage has been proposed as a possible cause of heavy isotope (56Fe) enrichment in the liver, no speciation and stable isotope ratio coupling data are available. Here, we report the δ56Fe values measured by multicollector ICP-MS and the result of Fe K-edge X-ray absorption near-edge structure (XANES) analysis of multiple tissues obtained from a skipjack tuna (Katsuwonus pelamis) and a chub mackerel (Scomber japonicus). Apparent isotopic fractionation between the liver and the muscle samples (Δ56FeL–M = δ56Feliver − δ56Femuscle) from these species was observed (0.85 ‰ and 0.57 ‰, respectively). The dominant Fe species in the muscle was heme Fe (the sum of methemoglobin, oxyhemoglobin, and deoxyhemoglobin), while ferritin was not detected according to the linear combination fitting of the XANES spectra. In the liver, ferritin contribution was ca. 28 %–54 % of the total Fe content. The apparent difference in δ56Fe between heme Fe and ferritin was estimated to range from 1.41 ‰ to 1.52 ‰ based on the tissue-specific δ56Fe values and the XANES results. These results indicate that the Fe storage as ferritin does not induce the lowering of δ56Fe in the muscle, considering the low contribution of the liver Fe to the total Fe content in the body.

Extremely low δ56Fe in arc tholeiites linked to ferrocarbonate recycling: Implications for Fe enrichment in the Awulale Arc, Central Asia

Recycling of Fe-rich materials through subduction may affect the element budgets and redox properties of the mantle, thus influencing the differentiation trends and mineralization types of mantle-derived magmas. However, the effects of different recycled Fe-rich materials on the mantle are dependent on their lithologies, which are still poorly constrained. Stable Fe isotopes can act as useful tracers for distinguishing among different recycled Fe-rich lithologies, and their imprints may be documented in mantle-derived magmas. This study focuses on the Fe isotopes of ferrobasalts and the associated dacites and magnetite ores in the Chagangnuoer Fe deposit of the Awulale Arc, Central Asia, to identify recycled Fe-rich materials and explore the Fe enrichment mechanism in continental arcs. Our results indicate that the ferrobasalts and dacites possess the lowest known δ56Fe, −0.40‰ ± 0.04‰ (2SE), among their counterparts worldwide. The low δ56Fe signatures are considered to originate from a hybridized mantle source, which may have been modified by recycled ferrocarbonates. The recycled ferrocarbonates may have melted during the decompressional heating stage of the slab subduction of the South Tianshan Ocean, coupled with asthenospheric upwelling under “wet” mantle conditions. The addition of ferrocarbonate melts to the mantle might have decreased the oxygen fugacity of the mantle wedge to below the fayalite−magnetite−quartz buffer, accounting for the Fe enrichment in arc tholeiites and large-scale Fe mineralization along the Awulale. Notably, our study reveals a novel carbonate recycling pathway in the cold subduction zones, where ferrocarbonates were subducted into the mantle and then recycled by the upwelling asthenosphere to mix with the fluid-metasomatized mantle through mantle convection.

Investigation of metasomatism using Cu, Zn and Fe stable isotopes: Rodingitization of mafic and ultramafic rocks in ophiolites from northern Greece

Rodingites, a high-Ca content variety of metasomatic rocks, have been found in the Veria-Naousa and Edessa ophiolites, in northern Greece. The rodingites from both areas are characterized by a substantial overprint of primary textures. Coupled field and petrographic observations reveal derivation from ultramafic and mafic protoliths. The mineral phases in the ultramafic-derived rodingites (UDR) include mainly diopside, garnet, chlorite, tremolite, and FeTi oxides whereas mafic-derived rodingites (MDR) contain diopside, garnet, vesuvianite, chlorite and quartz. Here we present, for the first time, whole rock Cu, Zn and Fe isotopic data for the UDR and MDR from the Veria-Naousa and Edessa ophiolites, to investigate the evolution of this peculiar metasomatic lithotype. All the studied rodingites present δ65Cu values varying from −0.17 ± 0.03‰ to +0.62 ± 0.05‰ and δ66Zn ranging from −0.06 ± 0.03‰ to +0.74 ± 0.06‰. 0.0. Copper isotope ratios are systematically heavier in rodingites compared to their respective protoliths whereas Zn shows a diverse behavior with enrichment in its light isotopes (group 1: comprising all the UDR and a MDR sample) or in its heavy isotopes (group 2, the rest MDR samples). The same gabbroic protolith can lead to both group 1 and 2 rodingites with respect to their Zn isotopic ratios. Alkaline conditions of the hydrothermal metasomatic fluids and the inferred sulfide and bisulfide ligands promoted mobility of Cu and Zn and have likely played a major role to their isotopic behavior in the rodingites. In contrast, Fe isotopes have not fractionated during rodingitization. Complex metasomatic processes, such as rodingitization, have a clear impact on stable isotope fractionation, which is decoupled between the Cu, Zn and Fe isotope systems. The lack of correlation between isotope ratios and any mineralogical or elemental indicator highlights the absence of any profound relationship between isotope fractionation and mineral phases, which could reflect the stage and evolution of rodingitization. The consistent isotopic behavior of Cu indicates a promising geochemical tool to distinguish metasomatized and non-metasomatized samples within different observed groups, and define conditions and parameters during Ca-metasomatism, regardless the degree of rodingitization, prior alteration and various protoliths compositions. Additionally, Zn isotopes give a useful insight on the metasomatic conditions for both ultramafic and mafic precursors defining local pH changes coupled with available ligands, HS−, where Cu isotopes alone would not be able to describe.

Iron Isotopes in Acid Mine Drainage: Extreme and Divergent Fractionation between Solid (Schwertmannite, Jarosite, and Ferric Arsenate) and Aqueous Species.

Examination of stable Fe isotopes is a powerful tool to explore Fe cycling in a range of environments. However, the isotopic fractionation of Fe in acid mine drainage (AMD) has received little attention and is poorly understood. Here, we analyze Fe isotopes in waters and Fe(III)-rich solids along an AMD flow-path. Aqueous Fe spanned a concentration and δ56Fe range of ∼420 mg L-1 and + 0.04‰ at the AMD source to ∼100 mg L-1 and -0.81‰ at ∼450 m downstream. Aqueous As (up to ∼33 mg L-1) and SO42- (up to ∼2000 mg L-1), like aqueous Fe, decreased in concentration down the flow-path. X-ray absorption spectroscopy indicated that downstream attenuation in aqueous Fe, As, and SO42- was due to the precipitation of amorphous ferric arsenate (AFA), schwertmannite, and jarosite. The Fe(III) in these solids displayed extreme variability in δ56Fe, spanning +3.95‰ in AFA near the AMD source to -1.34‰ in schwertmannite at ∼450 m downstream. Similarly, the isotopic contrast between solid Fe(III) precipitates and aqueous Fe (Δ56Feppt-aq) dropped along the flow-path from about +4.1 to -1.1‰. The shift from positive to negative Δ56Feppt-aq reflects divergence between competing equilibrium versus kinetic fractionation processes.

Large Fractionation in Iron Isotopes Implicates Metabolic Pathways for Iron Cycling in Boreal Shield Lakes.

Stable Fe isotopes have only recently been measured in freshwater systems, mainly in meromictic lakes. Here we report the δ56Fe of dissolved, particulate, and sediment Fe in two small dimictic boreal shield headwater lakes: manipulated eutrophic Lake 227, with annual cyanobacterial blooms, and unmanipulated oligotrophic Lake 442. Within the lakes, the range in δ56Fe is large (ca. -0.9 to +1.8‰), spanning more than half the entire range of natural Earth surface samples. Two layers in the water column with distinctive δ56Fe of dissolved (dis) and particulate (spm) Fe were observed, despite differences in trophic states. In the epilimnia of both lakes, a large Δ56Fedis-spm fractionation of 0.4-1‰ between dissolved and particulate Fe was only observed during cyanobacterial blooms in Lake 227, possibly regulated by selective biological uptake of isotopically light Fe by cyanobacteria. In the anoxic layers in both lakes, upward flux from sediments dominates the dissolved Fe pool with an apparent Δ56Fedis-spm fractionation of -2.2 to -0.6‰. Large Δ56Fedis-spm and previously published metagenome sequence data suggest active Fe cycling processes in anoxic layers, such as microaerophilic Fe(II) oxidation or photoferrotrophy, could regulate biogeochemical cycling. Large fractionation of stable Fe isotopes in these lakes provides a potential tool to probe Fe cycling and the acquisition of Fe by cyanobacteria, with relevance for understanding biogeochemical cycling of Earth's early ferruginous oceans.

Coexisting Goethite Promotes Fe(II)-Catalyzed Transformation of Ferrihydrite to Goethite.

In redox-affected soil environments, electron transfer between aqueous Fe(II) and solid-phase Fe(III) catalyzes mineral transformation and recrystallization processes. While these processes have been studied extensively as independent systems, the coexistence of iron minerals is common in nature. Yet it remains unclear how coexisting goethite influences ferrihydrite transformation. Here, we reacted ferrihydrite and goethite mixtures with Fe(II) for 24 h. Our results demonstrate that with more goethite initially present in the mixture more ferrihydrite turned into goethite. We further used stable Fe isotopes to label different Fe pools and probed ferrihydrite transformation in the presence of goethite using 57Fe Mössbauer spectroscopy and changes in the isotopic composition of solid and aqueous phases. When ferrihydrite alone underwent Fe(II)-catalyzed transformation, Fe atoms initially in the aqueous phase mostly formed lepidocrocite, while those from ferrihydrite mostly formed goethite. When goethite was initially present, more goethite was formed from atoms initially in the aqueous phase, and nanogoethite formed from atoms initially in ferrihydrite. Our results suggest that coexisting goethite promotes formation of more goethite via Fe(II)–goethite electron transfer and template-directed nucleation and growth. We further hypothesize that electron transfer onto goethite followed by electron hopping onto ferrihydrite is another possible pathway to goethite formation. Our findings demonstrate that mineral transformation is strongly influenced by the composition of soil solid phases.

Iron isotope systematics during igneous differentiation in lavas from Kīlauea and Mauna Loa, Hawai'i

The Big Island of Hawai'i is currently the most active site of magmatic activity in the Hawaiian chain of volcanoes that are associated with a mantle plume in the Pacific Ocean. Mantle source variability and magmatic processes have both been proposed to significantly affect lava chemistry on the Big Island, which is most prominently illustrated in a radiogenic isotope dichotomy of the so-called ‘Kea’ and ‘Loa’ trends. Here, we present stable Fe isotopes (δ57Fe), complemented by radiogenic 176Hf/177Hf, in lavas from the Puʻu ʻŌʻō vent on the East Rift Zone of Kīlauea (Kea trend) and from the Southwest Rift Zone from Mauna Loa (Loa trend). In Hf isotopic space, lavas range from εHf = +8 to +13, with Puʻu ʻŌʻō samples aligning with published values of lavas from the ‘Kea-trend’ in SrHf isotope space, whereas Mauna Loa basalts and picrites presented here coincide with values of the Loa-trend. The Puʻu ʻŌʻō lavas have average δ57Fe of +0.15 ‰ and an average of MgO ~ 7 wt%. Mauna Loa basalts and picrites show on average lighter δ57Fe of +0.06 ‰ but higher MgO ~ 16 wt%. Combined, in a global OIB comparison, the Hawaiian samples have among the lowest δ57Fe reported to date. Both Puʻu ʻŌʻō and Mauna Loa lavas lie on a trend of decreasing δ57Fe with increasing MgO that is ascribed to olivine fractionation and accumulation. Geochemical indices of partial melting (e.g., (Gd/Yb)PM, TiO2) do not align with Fe isotopic signatures, whether corrected for crystal fractionation or not, and can thus not explain the heavy Fe isotopic signatures observed here. Likewise, a lack of co-variations of radiogenic isotopes with Fe isotopes do not support source inheritance from enriched, crustal-like plume components as the dominant process to explain the Fe isotopic signatures. On a three‑iron isotope plot, it appears that kinetic in combination or in exchange with equilibrium fractionation of stable isotopes can account for Fe isotopes lighter than δ57Fe < +0.15 ‰. An inherently heavy Fe isotope signature (> 0.15 ‰) is required to explain some of the high values measured here for which no geochemical proxy can be identified. Assuming fast recharge into the plumbing systems feeding Puʻu ʻŌʻō and Mauna Loa lavas with no presumed homogenisation in subsurface magma chambers, we surmise that the Hawaiian samples are reflecting lavas that experienced a combination of kinetic and equilibrium processes, which ultimately lead to a seemingly random distribution of Fe isotopes. The exposure to different magmatic processes, e.g., re-charging events, and the missing covariation between MgO vs δ57Fe argue for an open magma chamber underneath Puʻu ʻŌʻō and Mauna Loa, masking processes that influence Fe isotopes, i.e., source inheritance or melting degree. From our new stable Fe isotope data, we show that lavas, which travel through a plumbing system, can undergo multiple fractionation processes.

Iron Bioavailability from Ferrous Ammonium Phosphate, Ferrous Sulfate, and Ferric Pyrophosphate in an Instant Milk Drink-A Stable Isotope Study in Children.

Ferrous ammonium phosphate (FAP) is an iron salt that has been developed for the fortification of food matrices sensitive to color and flavor changes. The objective of the study was to measure iron absorption from FAP in young children and compare it to a previous evaluation of FAP in young women. A double-blind randomized crossover study with two parallel arms was used to evaluate the iron absorption from FAP added to reconstituted milk powder in comparison to that from ferrous sulfate (FeSO4) and ferric pyrophosphate (FePP). Iron absorption was measured in 39 children aged 3- to 6-years-old using erythrocyte incorporation of stable Fe isotopes (57Fe, 58Fe). The geometric mean iron absorption in iron replete children from FAP, FeSO4 and FePP from milk was 8.3%, 7.6% and 2.1%, respectively. Iron absorption from FAP and FeSO4 fortified milk was not significantly different (p = 0.199); however, it was significantly higher than from FePP fortified milk (p < 0.001). Iron bioavailability from FAP and FePP relative to FeSO4 (relative bioavailability (RBV)) was 110% and 33%, respectively. The RBV of FAP (110%) in iron replete children was higher than previously reported RBV (71%) in mainly iron deficient women. The difference in iron status between the children and women in the respective studies may explain the different RBV values and is discussed.

Evaluation of contribution of Fe in aerosols from different sources to the surface ocean based on Fe stable isotope ratio

Evaluation of contribution of Fe in aerosols from different sources to the surface ocean based on Fe stable isotope ratio

Geochemical evolution of the Rabaul volcanic complex, Papua New Guinea - Insights from HFSE, Sr-Nd-Hf, and Fe isotopes

The Rabaul volcanic complex, Papua New Guinea, is among the few calderas worldwide with ongoing volcanic activity. Its volcanic lithologies vary from mafic lavas from outer caldera cones to differentiated lavas within. In this study, representative lavas have been analysed for their major and trace element concentrations and radiogenic Sr-Nd-Hf isotope compositions to study the geochemical evolution of the magmatic system. Stable Fe isotopes and concentrations of high field strength elements (HFSE) complement the analyses as novel tools to assess the effect of high-temperature fractional crystallisation during ongoing differentiation. Major element systematics reveal a typical fractional crystallisation sequence of olivine, pyroxene, and plagioclase as the critical process controlling the magmatic evolution. A distinct increase of Zr/Hf from the basaltic (older) outer caldera lavas (~39) to the dacitic (younger) inner caldera lavas (~41–44) can be explained by fractionation of clinopyroxene and amphibole. Ratios of Nb/Ta tend to decrease with an increasing degree of differentiation, consistent with fractional crystallisation of amphibole but not clinopyroxene. Additional fractionation of Ti-magnetite and rather oxidising conditions are further supported by the Fe isotope compositions in the inner caldera lavas (δ57Fe from +0.03 to +0.22‰, ±0.04‰, 2 SD). The high Nb/Ta in more primitive outer caldera samples are coupled with increasing rare earth elements (REE) abundances, and slab melt-like subduction components can explain high Sr/Y and GdN/YbN in the magma sources. Complementary enrichments in fluid-mobile trace elements indicate that slab dehydration controlled the sub-arc enrichment of the inner caldera volcanism. Coupled Hf-Nd isotope compositions reveal the presence of the Indian-Australian mantle domain beneath Rabaul and a temporal trend towards sediment melt components overprinting inner caldera lavas. In conclusion, geochemical features show a temporal evolution controlled by (i) variable influence of partial slab melts vs slab fluids and (ii) a change in fractional crystallisation patterns from solely olivine and pyroxene-controlled to increasingly titano-magnetite and amphibole-controlled fractionation.

Contribution of combustion Fe in marine aerosols over the northwestern Pacific estimated by Fe stable isotope ratios

Abstract. The source apportionment of aerosol iron (Fe), including natural and combustion Fe, is an important issue because aerosol Fe can enhance oceanic primary production in the surface ocean. Based on our previous finding that combustion Fe emitted by evaporation processes has Fe isotope ratios (δ56Fe) that are approximately 4 ‰ lower than those of natural Fe, this study aimed to distinguish aerosol Fe sources over the northwestern Pacific using two size-fractionated marine aerosols. The δ56Fe values of fine and coarse particles from the eastern or northern Pacific were found to be similar to each other, ranging from 0.0 ‰ to 0.4 ‰. Most of them were close to the crustal average, suggesting the dominance of natural Fe. On the other hand, particles from the direction of East Asia demonstrated lower δ56Fe values in fine particles (−0.5 ‰ to −2.2 ‰) than in coarse particles (on average −0.02 ± 0.12 ‰). The correlations between the δ56Fe values and the enrichment factors of lead and vanadium suggested that the low δ56Fe values obtained were due to the presence of combustion Fe. The δ56Fe values of the soluble component of fine particles in this region were lower than the total, indicating the preferential dissolution of combustion Fe. In addition, we found a negative correlation between the δ56Fe value and the fractional Fe solubility in air masses from the direction of East Asia. These results suggest that the presence of combustion Fe is an important factor in controlling the fractional Fe solubility in air masses from the direction of East Asia, whereas other factors are more important in the other areas. By assuming typical δ56Fe values for combustion and natural Fe, the contribution of combustion Fe to the total (acid-digested) Fe in aerosols was estimated to reach up to 50 % of fine and 21 % of bulk (coarse + fine) particles in air masses from the direction of East Asia, whereas its contribution was small in the other areas. The contribution of combustion Fe to the soluble Fe component estimated for one sample was approximately twice as large as the total, indicating the importance of combustion Fe as a soluble Fe source despite lower emissions than the natural. These isotope-based estimates were compared with those estimated using an atmospheric chemical transport model (IMPACT), in which the fractions of combustion Fe in fine particles, especially in air masses from the direction of East Asia, were consistent with each other. In contrast, the model estimated a relatively large contribution from combustion Fe in coarse particles, probably because of the different characteristics of combustion Fe that are included in the model calculation and the isotope-based estimation. This highlights the importance of observational data on δ56Fe for size-fractionated aerosols to scale the combustion Fe emission by the model. The average deposition fluxes of soluble Fe to the surface ocean were 1.4 and 2.9 nmol m−2 d−1 from combustion and natural aerosols, respectively, in air masses from the direction of East Asia, which suggests that combustion Fe could be an important Fe source to the surface seawater among other Fe sources. Distinguishing Fe sources using the δ56Fe values of marine aerosols and seawater is anticipated to lead to a more quantitative understanding of the Fe cycle in the atmosphere and surface ocean.

Alkalinity of ocean island lavas decoupled from enriched source components: A case study from the EM1-PREMA Tasmantid mantle plume

The alkalinity of ocean island basalts (OIB), which form by upwelling thermo-chemical instabilities in the mantle, is often associated with the degree of melting. Yet it remains to be tested if alkalinity and the degree of melting are systematically associated with enriched mantle components. The Tasmantid Seamounts, which are fossil remnants of the Tasmantid mantle plume, comprise a north-south age-progressive submarine volcanic chain in the Coral and Tasman Seas East of Australia. Dredged seafloor lavas from nine seamounts along the seamount chain, ranging in age from 50 to 6.5 Ma, show a dichotomy in alkalinity, similar to those observed in other hotspot areas such as Hawai’i or Pitcairn. In radiogenic Sr-Nd-Hf-Pb isotope systematics, Tasmantid Seamount lavas form a continuum between EM1 and PREMA and are thus part of the prevalent EM1-PREMA association in the Pacific. However, their radiogenic Pb isotope systematics mark the Tasmantid plume as an individuum with no resemblance to any other plume. In stable Fe isotopes (expressed as δ57FePrim, which is the Fe isotopic composition calculated to primitive lavas along a liquid line of descent) alkali basalts are, on average, isotopically heavier than tholeiitic lavas, ranging in δ57FePrim from +0.10 to +0.21‰, unrelated to radiogenic isotope systematics, but with co-variations of δ57FePrim and Ti* (which is the primitive melt Ti content). These systematics point towards residual garnet as a key factor and thus indicate a solely petrologic relation between degrees of melting and Fe isotopes. Tholeiitic lavas exhibit a near-depleted mantle like isotopic composition (ranging in δ57FePrim from −0.01 to +0.22‰, median at δ57FePrim + 0.04‰), yet with values of up to δ57FePrim + 0.22‰ that require an isotopically heavy source of unknown origin.The lack of systematics between alkalinity and radiogenic isotope signatures indicates that temperature is the likely driving force for variable melting degrees in some samples over others. Based on these observations, we surmise that tholeiitic lavas form in the plume centre whereas alkaline lavas form at the cooler rim of the conduit. Mixing between melts and associated enriched components in the Tasmantid mantle plume may occur but, at least for alkaline lavas, only on a small scale.

An iron isotope perspective on back-arc basin development: Messages from Mariana Trough basalts

The geology and magmatism of the northern Mariana Trough (NMT) represent a type example for the development of a back-arc basin (BAB). It is a mature spreading center in the south and propagating northward via rifting of arc and rear arc lithosphere in response to trench retreat and overriding plate extension in space and time. It is thus essential to fully characterize its tectonomagmatic processes that are potentially of global significance. For this reason, we carried out a comprehensive geochemical study on basaltic samples (glasses) from the NMT axis from 17 to 23°N by analyzing a full suite of major and trace elements, Sr–Nd–Pb–Hf radiogenic isotopes and stable Fe isotopes. The Fe isotopes, in particular, have the potential to offer novel perspectives beyond the aforementioned geochemical variables. From south to north, the δ56Fe of the NMT basalts (NMTB) decrease systematically, varying from a MOR-like value of +0.12‰ to an arc-like value of 0.00‰. Importantly, incompatible element abundances and Sr–Nd–Pb–Hf isotope compositions of the NMTB also show systematic along-latitude variations. Positively correlated with δ56Fe, the abundances of fluid-insoluble elements (e.g., Nb, Ta, Zr, Hf, Ti and heavy rare earth elements) show the south-to-north decrease, suggesting that the NMTB δ56Fe systematics are inherited from the magma source variation. The source variation is most consistent with an asthenosphere source in the south and progressively more depleted harzburgitic lithosphere source of prior melt depletion towards north. On the other hand, there are scattered but significant enrichment trends towards north in terms of Sr–Nd–Pb–Hf radiogenic isotopes and fluid-soluble incompatible elements (e.g., Ba, Rb, Cs, Th, U, K, Pb, Sr and light rare earth elements), which is consistent with south-to-north increase in slab material (e.g., slab fluids, sediments etc.) contribution. These north-to-south magma source systematics defined by the NMTB can be readily understood as a tectonic response to the back-arc basin development with time from initial arc-magmatism dominated by sub-arc lithospheric mantle melting with significant slab material contributions to back-arc rifting and to back-arc spreading center magmatism characterized by increasing asthenospheric mantle melting, decreasing slab material contribution and diminishing sub-arc lithospheric mantle participation. This tectonic-magma source evolution in space and time is manifested by the snapshot of the NMTB magmatism in terms of the geology, petrology and geochemistry.The NMTB δ56Fe values and fluid-insoluble incompatible element abundances are unaffected by slab materials, but controlled by the harzburgitic residues of previous melt extraction depleted in these elements with low δ56Fe at the early arc-magmatism stage in the north and by the asthenosphere of MORB mantle characteristics in the south with well-developed back-arc spreading system. Importantly, these observations affirm the understanding that compositionally depleted and physically buoyant lithosphere is prerequisite as the overriding plate for subduction initiation at its edges.

Geochemical and isotopic constraints on the dynamics of the Earth: a Special Issue dedicated to Jan Dirk Kramers and his legacy to geochemistry

Chromium exists in two oxidation states Cr2+ and Cr3+ during high-temperature magmatic processes and changes in Cr redox are often associated with stable isotopic fractionation. Thus, the stable chromium isotope compositions of mantle-derived magmas bear the potential to trace the oxidation states of their mantle sources as well as any post melting changes in Cr redox (e.g. during magmatic differentiation), in a manner similar to magmatic stable Fe isotopic fractionation. However, these stable isotope fractionation effects are less understood for Cr relative to Fe. Komatiites and tholeiitic basalts represent a wide range of mantle-derived partial melts with variable fractional crystallization of phases with different affinity for Cr2+ and Cr3+. Thus, they offer potential archives to better understand high-temperature Cr isotope fractionation processes and mantle redox.Here, we report major and trace elements as well as coupled stable Cr and Fe isotope compositions of two well-characterized Archean komatiite-tholeiite suites from the Barberton Greenstone Belt, South Africa and Eswatini, and Belingwe Greenstone Belt, Zimbabwe. The sample suites range in MgO concentrations from 3.85 to 34.33 wt%, which allows investigation of the impact of large degrees of magmatic differentiation in a komatiite-basalt system. Whole-rock δ53/52CrSRM979 and δ56/54FeIRMM014 values range from −0.390 ± 0.016 to −0.061 ± 0.016‰ and −0.014 ± 0.018 to +0.192 ± 0.018‰, respectively. The komatiites have a very narrow range in their Cr isotopic composition with an average δ53/52CrSRM979 value of −0.122 ± 0.050‰ (2SD; n = 21), which supports previous estimates of the bulk silicate Earth δ53/52CrSRM979 value. However, high-Mg tholeiites and basaltic andesites exhibit significantly lighter δ53/52CrSRM979 and heavier δ56/54FeIRMM014 values than komatiites. These variations can be linked to crystallization and accumulation of mineral phases observed from fractionation trends of the two Archean komatiite-tholeiite suites. In detail, during crystallization and accumulation of olivine the Cr isotope compositions of komatiites stay invariant, whereas at the onset of Cr-bearing spinel and pyroxene crystallization the Cr isotope signatures of komatiitic basalts, high-Mg tholeiites and basaltic andesites become progressively lighter, which is attributed to the preferential incorporation of isotopically heavier Cr3+ in these mineral phases. The gradual increase of δ56/54FeIRMM014 with increasing magmatic differentiation, does not allow identifying the crystallization of particular mineral phases using Fe isotopes alone. Ultimately, this study demonstrates the power of combining stable Cr and Fe isotopic analyses to examine the effects of fractional crystallization on modifying melt source values and thus to ensure accurate mantle redox estimations.

Iron supplementation in anemic Zanzibari toddlers is associated with greater loss in erythrocyte iron isotope enrichment

Heavy parasitic loads increase the risk of iron (Fe) deficiency anemia, which remains prevalent globally. Where parasites are common, understanding the influence of parasitic infections on Fe incorporation and erythropoiesis in toddlers is especially important. The aim of this study was to identify the impacts of malarial and helminth infections on red blood cell (RBC) Fe incorporation and subsequent changes in RBC Fe isotope enrichment for 84 days postdosing in toddlers at high risk for parasitic infections. Fe incorporation was measured in a group of Zanzibari toddlers (n=71; 16-25 months) using a stable Fe isotopic method. At study entry, an oral stable Fe isotope was administered. Blood was collected 14 (D14) and 84 (D84) days postdosing for the assessment of Fe status indicators and RBC isotopic enrichment. Blood and stool samples were collected and screened for malaria and helminth parasites. Factors associated with changes in RBC Fe isotope enrichment were identified using regression models. Toddlers who had larger weight-for-age z-scores, lower total body Fe, and helminth infections (n=26) exhibited higher RBC Fe incorporation. RBC Fe isotope enrichment decreased from D14 to D84 by -2.75 percentage points (P<0.0001; n=66). Greater loss in RBC Fe isotope enrichment from D14 to D84 was observed in those who received Fe supplementation, those with either helminths or both malarial and helminth infections, and in those with greater RBC Fe incorporation on D14. Toddlers who received Fe supplementation exhibited significantly greater losses of RBC Fe isotope enrichment over time. We speculate this greater loss of RBC Fe enrichment is indicative of increased erythropoiesis due to the provision of Fe among anemic or helminth-infected toddlers.