Search

Abstract Modern Fe‐Si oxyhydroxide deposits occur in global marine hydrothermal vent sites. Despite their role as biogenic substrates and potential ore resources, much remains unknown about their formation processes. Here, we apply analyses of major and trace elements as well as Sr‐Nd‐Pb‐Fe isotopes combined with 238U‐230Th dating to Fe‐Si oxyhydroxides obtained from several hydrothermal fields along the Southwest Indian Ridge. These mineralized oxyhydroxides primarily consist of poorly crystalline two‐line ferrihydrite and amorphous opal‐A, with lesser amounts of nontronite and birnessite. The ubiquitous and characteristic Fe‐rich ultrastructures in the oxyhydroxides directly indicate microbial activity. The 238U‐230Th dating constrains their crystallization ages from ca. 11,873 to 384 years old. The seawater‐like 87Sr/86Sr and varying 143Nd/144Nd ratios underline a high proportion of seawater mixed with hydrothermal fluids. The radiogenic Pb isotopic patterns suggest a primary derivation of Pb leached from substrate basalts and to a lesser extent Pb from seawater. Stable iron isotopic compositions for different oxyhydroxides display a remarkable range between −1.47 and 0.82‰, which were interpreted as reflecting the fractionation processes during the formation of the deposits under evolving depositional redox conditions. The partial oxidation of Fe(II) and the subsurface removal of isotopically heavy Fe oxyhydroxides are suggested to play a vital role in shifting the Fe isotopic signature toward more negative values. Given that these Fe‐Si oxyhydroxide deposits exhibit features similar to certain ancient iron formations (IFs), Fe isotope systematics of these deposits may hold significant potential for fingerprinting the biological Fe oxidation processes that drove IF deposition on early Earth.

The Ediacaran age (ca. 570 Ma) Shuram excursion, a ca. $12‰$ depletion in $\delta ^{13}\mathrm{C}_{\mathrm{carb}}$, may record a dramatic oxidation of marine sediments associated with a reorganization of Earth’s carbon cycle closely preceding the rise of large metazoans. However, several geochemical indicators suggest it may instead record secondary processes affecting the sediments such as post-depositional alteration. The stable isotopic composition of iron incorporated within carbonates $(\delta ^{56}\mathrm{Fe}_{\mathrm{carb}})$ reveals an anomalous $^{56}\mathrm{Fe}$-depletion (down to $-1.05‰$) in strata containing the Shuram excursion, while the underlying and overlying strata have crustal $\delta ^{56}\mathrm{Fe}_{\mathrm{carb}}$ values. These depleted $\delta ^{56}\mathrm{Fe}_{\mathrm{carb}}$ data during the Shuram excursion reflect incomplete reduction of iron oxides, limited by low ambient organic carbon contents. This elevated pulse of sedimentary iron oxides would consume the majority of the limited pool of organic carbon and therefore would give rise to very low net organic carbon burial during a time of enhanced detrital delivery of oxidized iron to the sediments. These results imply a syndepositional origin for the Shuram excursion, which represents a shift in the redox composition of Earth’s sedimentary shell toward more oxidizing conditions, perhaps removing a long-lived buffer on atmospheric oxygen.

Lavas produced at subduction zones represent the integration of both source heterogeneity and an array of crustal processes, such as: differentiation; mixing; homogenisation; assimilation. Therefore, unravelling the relative contribution of the sub-arc mantle source versus these crustal processes is difficult when using the amalgamated end products in isolation. In contrast, plutonic xenoliths provide a complementary record of the deeper roots of the magmatic plumbing system and provide a unique record of the true chemical diversity of arc crust. Here, we present the δ56Fe record from well characterised plutonic xenoliths from two distinct volcanic centres in the Lesser Antilles volcanic arc–the islands of Martinique and Statia. The primary objective of this study is to test if the Fe isotope systematics of arc lavas are controlled by sub-arc mantle inputs or during subsequent differentiation processes during a magma’s journey through volcanic arc crust. The Fe isotopic record, coupled to petrology, trace element chemistry and radiogenic isotopes of plutonic xenoliths from the two islands reveal a hidden crustal reservoir of heavy Fe that previously hasn’t been considered. Iron isotopes are decoupled from radiogenic isotopes, suggesting that crustal and/or sediment assimilation does not control the Fe systematics of arc magmas. In contrast to arc lavas, the cumulates from both islands record MORB-like δ56Fe values. In Statia, δ56Fe decreases with major and trace element indicators of differentiation (SiO2, Na2O + K2O, Eu/Eu*, Dy/Yb), consistent with fractionating mineral assemblages along a line of liquid descent. In Martinique, δ56Fe shows no clear relationship with most indicators of differentiation (apart from Dy/Yb), suggesting that the δ56Fe signature of the plutonic xenoliths has been overprinted by later stage processes, such as percolating reactive melts. Together, these data suggest that magmatic processes within the sub-arc crust overprint any source variation of the sub-arc mantle and that a light Fe source is not a requirement to produce the light Fe isotopic compositions recorded in volcanic arc lavas. Therefore, whenever possible, the complimentary plutonic record should be considered in isotopic studies to understand the relative control of the mantle source versus magmatic processes in the crust.

Dissolved iron (Fe) isotopes in river water have a pivotal role in understanding the Fe cycle in the surficial environment. A total of 13 samples of river water were collected from the Mun River to analyze the Fe isotopes and their controlling factors in river water, such as dissolved organic carbon (DOC) and different supply sources. The results showed that dissolved Fe (DFe) concentrations ranged from 21.49 μg/L to 232.34 μg/L in the dry season and ranged from 10.48 μg/L to 135.27 μg/L in the wet season, which might be ascribed to the dilution effect. The δ56Fe of the dry season (−0.34 to 0.57‰, with an average 0.09‰) was lower than that of the wet season (−0.15 to 0.48‰, with an average 0.14‰). Combined with the δ56Fe and DFe/DAl ratios, the end-members of DFe were identified, including rock weathering (high δ56Fe and low DFe/DAl ratio), anthropogenic inputs (high δ56Fe and high DFe/DAl ratio) and groundwater inputs (low δ56Fe and low DFe/DAl ratio). The relationship between δ56Fe and DOC concentrations suggested that the chelation of organic matter with heavy Fe isotopes was one of the important sources of heavy Fe isotopes in river water.

Layered mafic-ultramafic intrusions (LMI) are among the largest igneous bodies on Earth, and represent aggregations of large volumes of mantle- and some crustal-derived melts. Melts are emplaced over time-intervals of less than 1 million years, predominantly through multiple pulses of injections into pre-existing melt-crystal slurries. The dynamic interaction of physical processes, including density-driven separation and mixing of different components, within a solidifying magma chamber leads to such extreme chemical diversity between cumulate rock units that no unified model currently explains all aspects of the genesis of these intrusions. Here we present whole-rock stable Fe isotope data (expressed in ‰ variations as δ57Fe relative to IRMM-014) for samples of drill core taken from the stratified paleo-magma chamber of the Upper Zone of the late-Archean Windimurra Igneous Complex, Western Australia. Variations from near chondritic (δ57Fe ∼ + 0‰) to heavy (δ57Fe∼ + 0.2‰) values show a co-variation with initial radiogenic Hf isotope data that is unique to the Windimurra Upper Zone. The systematic isotopic variations from the roof to the base of the Upper Zone are best explained by an intricate sequence of events that included fractional crystallization and physical mixing. We propose that melt freshly sourced from the mantle was injected into and inflated a pre-existing crystal-melt mush comprising the upper Middle Zone. Re-establishment of crystal layering after replenishment introduced a chemical stratification with the formation of what became the Upper Zone and a crystal-interstitial melt ratio decreasing from roof to base. Basal, vanadiferous magnetitite horizons crystallized from Fe out of the liquid-in-residence. Variable degrees of perturbation and chaotic stirring of crystals with imperfect mixing of new and old components was followed by rapid crystal settling and subsequent cumulate stratification. Such melt rejuvenation, proposed here to be the cause for a newly established Upper Zone, leaves no unique petrologic fingerprint and forges a range in hybrid magma compositions throughout the Upper Zone rather than one single parental melt. This incremental growth of the intrusion can explain not only the observed coupled Fe-Hf isotope systematics, but also mineral disequilibria and cryptic layering in layered intrusions. In the context of incremental pluton assembly, two-component mixing paired with source heterogeneity can, at least in parts, potentially explain zircon-hosted Hf isotope heterogeneity so often observed in larger magmatic bodies.