Iron Isotope Variations in Coastal Seawater Determined by Multicollector ICP-MS

In this paper, we applied a reliable technique for measuring Fe isotope variations in coastal seawater at nanomolar levels. Iron was directly pre-concentrated from acidified seawater samples onto a nitrilotriacetic acid chelating resin and further purified using anion-exchange resin. Sample recovery, determined using a standard addition method, was essentially quantitative. Iron was then determined using a high-resolution multicollector ICP-MS (Neptune) coupled to an ApexQ desolvation introduction system. The external precision for δ⁵⁶Fe values was 0.11‰ (2s) when using total a Fe quantity between 25 and 100 ng. We initially applied this technique to measure the Fe isotope composition of dissolved Fe from several coastal environments in the north-eastern United States and we observed a range of δ⁵⁶Fe values between -0.9‰ and 0.1‰ relative to the IRMM-14 reference material. Iron isotope compositions of several reference water materials for inter-laboratory comparisons were also reported. Our results suggest that iron in coastal seawater, derived from benthic diagenesis and/or groundwater has negative Fe isotopic signatures that are distinct from other iron sources such as atmospheric deposition and rivers.     

Iron isotope fractionation during biogeochemical cycle: Information from suspended particulate matter (SPM) in Aha Lake and its tributaries,Guizhou, China

Iron isotope compositions of suspended particulate matters (SPM) collected from the Aha Lake, an artificial lake in the karst area of Yun-Gui Plateau, and its tributaries in summer and winter were investigated for our understanding of the behavior of Fe isotopes during iron biogeochemical cycling in lake. δ⁵⁶Fe values of SPM display statistically negative shift relative to IRMM-014. Samples from the lake display a range from ?1.36‰ to ?0.10‰ in summer and from ?0.30‰ to ?0.07‰ in winter, while river samples vary from ?0.88‰ to 0.07‰ in summer and from ?0.35‰ to ?0.03‰ in winter. The average iron isotope composition of aerosol samples is + 0.10‰, which is very similar to that of igneous rocks (0.09‰). The SPM in most rivers and water column showed seasonal variation in δ⁵⁶Fe value: the δ⁵⁶Fe values of SPM in summer were lower than in winter. The seasonal variation in δ⁵⁶Fe value of the riverine SPM should be ascribed to the change in source of particulate Fe and geochemical process in the watershed: More particulate Fe was leached from soil and produced by weathering of pyrite widely distributed in coal-containing strata. It is suggested that both allochthonous inputs and the redox iron cycling control the variations of δ⁵⁶Fe values for SPM in lake.During summer stratification, an Fe cycle named “ferrous wheel” is established near the redox boundary where the upwardly diffusing Fe(II) is oxidized and the reactive Fe oxides formed will continuously sink back into the reduction zone to complete the cycle. The δ⁵⁶Fe values for SPM reach the minima, ?0.88‰ for DB station and ?1.36‰ for LJK station, just near the redox boundary as a result of the Fe cycling, where a rough 45% to 76% of Fe in these particles was produced by the repetitive cycle. Due to random transportation and diffusion, δ⁵⁶Fe values of the particles near the redox zone distributed into approximately a Gaussian shape. The good negative correlation existed between δ⁵⁶Fe values and Fe/Al ratios for DB station, suggesting that they together can be used as good indicators of the redox-driven Fe transformations.     

Iron Isotope Compositions of Natural River and Lake Samples in the Karst Area, Guizhou Province, Southwest China

To better understand the Fe isotope characteristics of natural samples in the Karst area, the Fe isotope compositions of riverine suspended particulates, lake suspended particulates, lake sediments, porewaters, phytoplanktons, and aerosols in the watersheds of Lake Aha (a mineralized water system) and Lake Hongfeng (a mesotrophic water system), which are located in the Karst area, southwest China, were investigated. The studied samples displayed a variable range between δ56Fe=?2.03‰ and 0.36‰. Aerosols and phytoplanktons have similar or slightly heavier Fe isotope compositions relative to the average of igneous rocks. Fe isotope compositions of riverine Suspended Particulate Matter (SPM) were mainly affected by the types of tributaries. Suspended particulates collected from tributaries seriously contaminated with coal mine drainages displayed negative δ56Fe values (?0.89‰ to ?0.31‰) during summer, and there were significant increases of δ56Fe values in winter, except AR2, which was polluted with both coal mine drainage and sewage effluent. Characteristics of lakes have important influences on Fe isotope compositions of suspended particulates, lake sediments, and porewaters. The epilimnetic particulate Fe of Lake Hongfeng had δ56Fe=?0.04‰ to 0.13‰, while lighter Fe isotope compositions were measured for particulate Fe from Lake Aha, ranging from ?0.42‰ to ?0.09‰. Sediments collected from Hou Wu (HW) station of Lake Hongfeng have an average δ56Fe value of 0.09‰ and their corresponding porewaters have lighter Fe isotope compositions, ranging from ?0.57‰ to ?0.31‰; no significant variations have been observed. For the Liang Jiang Kou (LJK) station of Lake Aha, the content of reactive Fe and the concentration of sulfate were all high. Due to the reactive Fe recycling, including dissimilatory Fe reduction, adsorption, and Fe–sulfide formation, porewaters sampled near the sediment surface have been found to have a δ56Fe value as low as ?2.03‰ and an increase up to 0.12‰, with a burial depth of 10?cm. In contrast, an opposite variation trend was found for LJK sediments. Sediments sampled at 1-cm depth had a value of δ56Fe=?0.59‰ and decrease as low as ?1.75‰ with burial depth. This investigation demonstrated that significant Fe isotope fractionations occur in surface environments. Fe isotope compositions of particulate Fe were seriously affected by Fe sources, and Fe biogeochemical recycling has an important influence on Fe isotope fractionations in lake sediments, especially when there are significant amounts of reactive Fe and sulfate.     

Two pulses of mineralization and genesis of the Zhaxikang Sb–Pb–Zn–Ag deposit in southern Tibet: Constraints from Fe–Zn isotopes

Zhaxikang is one large Sb–Pb–Zn–Ag deposit located in the North Himalaya of southern Tibet. To date, the genesis of this deposit still remains controversial. Here, we present new pyrite Fe and sphalerite Zn isotopic data for the first three stages of mineralization, Fe–Zn isotopic data for Mn–Fe carbonate that formed during the first two stages of mineralization, and Zn isotopic data for the slate wall rocks of the Jurassic Ridang Formation to discuss the genesis of the Zhaxikang deposit. The overall δ⁵⁶Fe and δ⁶⁶Zn values range from −0.80‰ to 0.43‰ and from −0.03‰ to 0.38‰, respectively. The δ⁵⁶Fe values of Mn–Fe carbonates are lighter than those of associated pyrite in six mineral pairs, indicating that the iron carbonates are preferentially enriched in light Fe isotopes relative to pyrite. The sphalerite has lighter δ⁶⁶Zn values than associated Mn–Fe carbonates in three mineral pairs.The δ⁵⁶Fe values of pyrite that formed during the first three stages of mineralization gradually increase from stage 1 (−0.33‰ to −0.09‰) through stage 2 (−0.30‰ to 0.19‰) to stage 3 (0.16‰–0.43‰). In comparison, the sphalerite that formed during these stages has δ⁶⁶Zn values that gradually decrease from stage 1 (0.16‰–0.35‰) through stage 2 (0.09‰–0.23‰) to stage 3 (−0.03‰ to 0.22‰). These data, in conjunction with the observations of hand specimens and thin sections, suggest that the deposit was overprinted by a second pulse of mineralization. This overprint would account for these Fe–Zn isotopic variations as well as the kinetic Rayleigh fractionation that occurred during mineralization. The temporally increasing δ⁵⁶Fe and decreasing δ⁶⁶Zn values recorded in the deposit are also coincident with an increase in alteration, again supporting the existence of two pulses of mineralization. The δ⁵⁶Fe values of the first pulse of ore-forming fluid were calculated using theoretical equations, yielding values of −0.54‰ to −0.34‰ that overlap with those of submarine hydrothermal solutions (−1‰ to 0‰). However, the δ⁵⁶Fe values of the stage 3 pyrite are heavier than those of typical submarine hydrothermal solutions, which suggests that the second pulse of mineralization was probably derived from a magmatic hydrothermal fluid. In addition, the second pulse of ore-forming fluid has brought some Fe and taken away parts of Zn, which results the lighter δ⁶⁶Zn values of sphalerite and heavier δ⁵⁶Fe values of pyrite from the second pulse of mineralization. Overall, the Zhaxikang deposit records two pulses of mineralization, and the overprint by the second pulse of mineralization causes the lighter δ⁶⁶Zn values and heavier δ⁵⁶Fe values of modified samples.     

Iron isotopic systematics of UHP eclogites respond to oxidizing fluid during exhumation

The iron stable isotope compositions (δ⁵⁶Fe) and iron valence states of ultrahigh‐pressure eclogites from Bixiling in the Dabie orogen belt, China, were measured to trace the changes of geochemical conditions during vertical transportation of earth materials, for example, oxygen fugacity. The bulk Fe³⁺/ΣFe ratios of retrograde eclogites, determined by Mössbauer spectroscopy, are consistently higher than those of fresh eclogites, suggesting oxidation during retrograde metamorphism and fluid infiltration. The studied eclogites (five samples) display limited mid‐ocean ridge basalts (MORB)‐like (~0.10‰) δ⁵⁶Fe values, which are indistinguishable from their protoliths, that is, gabbro cumulates formed through differentiation of mantle‐derived basaltic magma. This suggests that Fe isotope fractionation during continental subduction is limited. Garnet separates display limited δ⁵⁶Fe variation ranging from ?0.08 ± 0.07 ‰ to 0.02 ± 0.07‰, whereas coexisting omphacite displays a large variation of δ⁵⁶Fe values from 0.15 ± 0.07‰ to 0.47 ± 0.07‰. Omphacite also has highly variable Fe³⁺/ΣFe ratios from 0.367 ± 0.025 to 0.598 ± 0.024, indicating modification after peak metamorphism. Omphacite from retrograde eclogites has elevated Fe³⁺/ΣFe ratios (0.54–0.60) compared to that from fresh eclogites (~0.37), whereas garnet displays a narrow range of ferric iron content with Fe³⁺/ΣFe ratios from 0.039 ± 0.013 to 0.065 ± 0.022. The homogenous δ⁵⁶Fe values and Fe³⁺/ΣFe ratios of garnet suggest that it survived the retrograde metamorphism and preserved its Fe‐isotopic features and ferric contents of peak metamorphism. Because of similar diffusion rates of Fe and Mg in garnet and omphacite, and constant Δ²⁶Mg_{omphacite‐garnet} values (1.14 ± 0.04‰), equilibrium iron isotope fractionation between garnet and omphacite was probably achieved during peak metamorphism. Elevated Fe³⁺/ΣFe ratios of omphacite from retrograde eclogites and variant Δ⁵⁶Fe_{omphacite‐garnet} values of the studied eclogites (0.13 ± 0.10‰ to 0.48 ± 0.10‰) indicate that oxidized geofluid infiltration resulted in the elevation of δ⁵⁶Fe values of omphacite during retrograde metamorphism.     

Iron isotope fractionation in subduction-related high-pressure metabasites (Ile de Groix,France)

Characterisation of mass transfer during subduction is fundamental to understand the origin of compositional heterogeneities in the upper mantle. Fe isotopes were measured in high-pressure/low-temperature metabasites (blueschists, eclogites and retrograde greenschists) from the Ile de Groix (France), a Variscan high-pressure terrane, to determine if the subducted oceanic crust contributes to mantle Fe isotope heterogeneities. The metabasites have δ⁵⁶Fe values of +0.16 to +0.33‰, which are heavier than typical values of MORB and OIB, indicating that their basaltic protolith derives from a heavy-Fe mantle source. The δ⁵⁶Fe correlates well with Y/Nb and (La/Sm)_PM ratios, which commonly fractionate during magmatic processes, highlighting variations in the magmatic protolith composition. In addition, the shift of δ⁵⁶Fe by +0.06 to 0.10‰ compared to basalts may reflect hydrothermal alteration prior to subduction. The δ⁵⁶Fe decrease from blueschists (+0.19 ± 0.03 to +0.33 ± 0.01‰) to eclogites (+0.16 ± 0.02 to +0.18 ± 0.03‰) reflects small variations in the protolith composition, rather than Fe fractionation during metamorphism: newly-formed Fe-rich minerals allowed preserving bulk rock Fe compositions during metamorphic reactions and hampered any Fe isotope fractionation. Greenschists have δ⁵⁶Fe values (+0.17 ± 0.01 to +0.27 ± 0.02‰) similar to high-pressure rocks. Hence, metasomatism related to fluids derived from the subducted hydrothermally altered metabasites might only have a limited effect on mantle Fe isotope composition under subsolidus conditions, owing to the large stability of Fe-rich minerals and low mobility of Fe. Subsequent melting of the heavy-Fe metabasites at deeper levels is expected to generate mantle Fe isotope heterogeneities.     

白云鄂博地区相关地质单元的铁同位素特征及其对白云鄂博矿床成因的制约

白云鄂博Fe-REE-Nb矿床是世界著名的巨型多金属矿床,它的成因一直是个激烈争论的问题,观点主要集中在沉积成因和岩浆成因上,而铁的物质来源问题是争论的焦点之一。近年来Fe同位素的快速发展为解决白云鄂博铁矿的成因提供了新思路。对白云鄂博地区发育的白云鄂博群尖山组铁质板岩、宽沟北沉积型铁矿、腮林忽洞微晶丘、灰绿岩墙这些相关地质单元的Fe同位素组成特征进行了研究,为白云鄂博矿床成因研究提供了最直接的参考。结果表明,尖山组铁质板岩的δ56Fe值为-0.49‰～0.48‰,平均值为-0.03‰±0.84‰,2SD,n=5;宽沟北沉积型铁矿的δ56Fe值为-0.68‰～0.23‰,平均值为-0.10‰±0.78‰,2SD,n=5;腮林忽洞微晶丘δ56Fe值为-0.64‰～0.12‰,平均值为-0.28‰±0.57‰,2SD,n=6;辉绿岩的Fe同位素组成δ56Fe值集中在0.11‰～0.16‰。腮林忽洞微晶丘总体上比白云鄂博赋矿白云岩富集Fe的轻同位素,Fe同位素组成变化也相对更大,表明两者可能有不同的成因。白云鄂博地区尖山组铁质板岩、宽沟北沉积型铁矿与世界其他地区含铁沉积建造的Fe同位素组成类似,其共同特征是,Fe同位素变化较大,总体上δ56Fe大于0‰。这一特征与白云鄂博铁矿的Fe同位素组成差别较大。白云鄂博矿床的δ56Fe集中在0‰附近,与白云鄂博地区灰绿岩、世界不同地区火成岩和岩浆型铁矿的Fe同位素组成特征一致。表明白云鄂博铁矿可能不是沉积成因的,更有可能与岩浆作用有关。     

Iron isotope compositions of carbonatites record melt generation, crystallization, and late-stage volatile-transport processes

Carbonatites define the largest range in Fe isotope compositions yet measured for igneous rocks, recording significant isotopic fractionations between carbonate, oxide, and silicate minerals during generation in the mantle and subsequent differentiation. In contrast to the relatively restricted range in δ⁵⁶Fe values for mantle-derived basaltic magmas (δ⁵⁶Fe?=?0.0?±?0.1‰), calcite from carbonatites have δ⁵⁶Fe values between ?1.0 and +0.8‰, similar to the range defined by whole-rock samples of carbonatites. Based on expected carbonate-silicate fractionation factors at igneous or mantle temperatures, carbonatite magmas that have modestly negative δ⁵⁶Fe values of ~ ?0.3‰ or lower can be explained by equilibrium with a silicate mantle. More negative δ⁵⁶Fe values were probably produced by differentiation processes, including crystal fractionation and liquid immiscibility. Positive δ⁵⁶Fe values for carbonatites are, however, unexpected, and such values seem to likely reflect interaction between low-Fe carbonates and Fe³⁺-rich fluids at igneous or near-igneous temperatures; the expected δ⁵⁶Fe values for Fe²⁺-bearing fluids are too low to produced the observed positive δ⁵⁶Fe values of some carbonatites, indicating that Fe isotopes may be a valuable tracer of redox conditions in carbonatite complexes. Further evidence for fluid-rock or fluid-magma interactions comes from the common occurrence of Fe isotope disequilibrium among carbonate, oxide, silicate, and sulfide minerals in the majority of the carbonatites studied. The common occurrence of Fe isotope disequilibrium among minerals in carbonatites may also indicate mixing of phenocyrsts from distinct magmas. Expulsion of Fe³⁺-rich brines into metasomatic aureols that surround carbonatite complexes are expected to produce high-δ⁵⁶Fe fenites, but this has yet to be tested.     

The continental shelf benthic iron flux and its isotope composition

Benthic iron fluxes from sites along the Oregon-California continental shelf determined using in situ benthic chambers, range from less than 10 μmol m⁻² d⁻¹ to values in excess of ∼300 μmol m⁻² d⁻¹. These fluxes are generally greater than previously published iron fluxes for continental shelves contiguous with the open ocean (as opposed to marginal seas, bays, or estuaries) with the highest fluxes measured in the regions around the high-sediment discharge Eel River and the Umpqua River. These benthic iron fluxes do not covary with organic carbon oxidation rates in any systematic fashion, but rather seem to respond to variations in bottom water oxygen and benthic oxygen demand. We hypothesize that the highest rates of benthic iron efflux are driven, in part, by the greater availability of reactive iron deposited along these river systems as compared to other more typical continental margin settings. Bioirrigation likely plays an important role in the benthic Fe flux in these systems as well. However, the influence of bottom water oxygen concentrations on the iron flux is significant, and there appears to be a threshold in dissolved oxygen (∼60-80 μM), below which sediment-ocean iron exchange is enhanced. The isotope composition of this shelf-derived benthic iron is enriched in the lighter isotopes, and appears to change by ∼3‰ (δ⁵⁶Fe) during the course of a benthic chamber experiment with a mean isotope composition of −2.7 ± 1.1‰ (2 SD, n = 9) by the end of the experiment. This average value is slightly heavier than those from two high benthic Fe flux restricted basins from the California Borderland region where δ⁵⁶Fe is −3.4 ± 0.4‰ (2 SD, n = 3). These light iron isotope compositions support previous ideas, based on sediment porewater analyses, suggesting that sedimentary iron reduction fractionates iron isotopes and produces an isotopically light iron pool that is transferred to the ocean water column. In sum, our data suggest that continental shelves may export a higher efflux of iron than previously hypothesized, with the likelihood that along river-dominated margins, the benthic iron flux could well be orders of magnitude larger than non-river dominated shelves. The close proximity of the continental shelf benthos to the productive surface ocean means that this flux is likely to be essential for maintaining ecosystem micronutrient supply.     

A re-assessment of nickel-doping method in iron isotope analysis on rock samples using multi-collector inductively coupled plasma mass spectrometry

Element doping has been proved to be a useful method to correct for the mass bias fractionation when analyzing iron isotope compositions. We present a systematic re-assessment on how the doped nickel may affect the iron isotope analysis in this study by carrying out several experiments. We find three important factors that can affect the analytical results, including the Ni:Fe ratio in the analyte solutions, the match of the Ni:Fe ratio between the unknown sample and standard solutions, and the match of the Fe concentration between the sample and standard solutions. Thus, caution is required when adding Ni to the analyte Fe solutions before analysis. Using our method, the δ⁵⁶Fe and δ⁵⁷Fe values of the USGS standards W-2a, BHVO-2, BCR-2, AGV-2 and GSP-2 are consistent with the recommended literature values, and the long-term (one year) external reproducibility is better than 0.03 and 0.05‰ (2SD) for δ⁵⁶Fe and δ⁵⁷Fe, respectively. Therefore, the analytical method established in our laboratory is a method of choice for high quantity Fe isotope data in geological materials.

     

On the iron isotope heterogeneity of lithospheric mantle xenoliths: implications for mantle metasomatism, the origin of basalts and the iron isotope composition of the Earth

With the aim to better understand the cause of the iron isotope heterogeneity of mantle-derived bulk peridotites, we compared the petrological, geochemical and iron isotope composition of four xenolith suites from different geodynamic settings; sub-arc mantle (Patagonia); subcontinental lithospheric mantle (Cameroon), oceanic mantle (Kerguelen) and cratonic mantle (South Africa). Although correlations were not easy to obtain and remain scattered because these rocks record successive geological events, those found between δ⁵⁷Fe, Mg#, some major and trace element contents of rocks and minerals highlight the processes responsible for the Fe isotope heterogeneity. While partial melting processes only account for moderate Fe isotope variations in the mantle (<0.2 ‰, with bulk rock values yielding a range of δ⁵⁷Fe ± 0.1 ‰ relative to IRMM-14), the main cause of Fe isotope heterogeneity is metasomatism (>0.9 ‰). The kinetic nature of rapid metasomatic exchanges between low viscosity melts/fluids and their wall-rocks peridotite in the mantle is the likely explanation for this large range. There are a variety of responses of Fe isotope signatures depending on the nature of the metasomatic processes, allowing for a more detailed study of metasomatism in the mantle with Fe isotopes. The current database on the iron isotope composition of peridotite xenoliths and mafic eruptive rocks highlights that most basalts have their main source deeper than the lithospheric mantle. Finally, it is concluded that due to a complex geological history, Fe isotope compositions of mantle xenoliths are too scattered to define a mean isotopic composition with enough accuracy to assess whether the bulk silicate Earth has a mean δ⁵⁷Fe that is chondritic, or if it is ~0.1 ‰ above chondrites as initially proposed.     

High precision iron isotope measurements of terrestrial and lunar materials

We present the analytical methods that have been developed for the first high-precision Fe isotope analyses that clearly identify naturally-occurring, mass-dependent isotope fractionation. A double-spike approach is used, which allows rigorous correction of instrumental mass fractionation. Based on 21 analyses of an ultra pure Fe standard, the external precision (1-SD) for measuring the isotopic composition of Fe is ±0.14 ‰/mass; for demonstrated reproducibility on samples, this precision exceeds by at least an order of magnitude that of previous attempts to empirically control instrumentally-produced mass fractionation (Dixon et al., 1993). Using the double-spike method, 15 terrestrial igneous rocks that range in composition from peridotite to rhyolite, 5 high-Ti lunar basalts, 5 Fe-Mn nodules, and a banded iron formation have been analyzed for their iron isotopic composition. The terrestrial and lunar igneous rocks have the same isotopic compositions as the ultra pure Fe standard, providing a reference Fe isotope composition for the Earth and Moon. In contrast, Fe-Mn nodules and a sample of a banded iron formation have iron isotope compositions that vary over a relatively wide range, from δ⁵⁶Fe = +0.9 to −1.2 ‰; this range is 15 times the analytical errors of our technique. These natural isotopic fractionations are interpreted to reflect biological (“vital”) effects, and illustrate the great potential Fe isotope studies have for studying modern and ancient biological processes.     

Iron isotope variations in Holocene sediments of the Gotland Deep, Baltic Sea

Holocene sediments from the Gotland Deep basin in the Baltic Sea were investigated for their Fe isotopic composition in order to assess the impact of changes in redox conditions and a transition from freshwater to brackish water on the isotope signature of iron. The sediments display variations in δ⁵⁶Fe (differences in the ⁵⁶Fe/⁵⁴Fe ratio relative to the IRMM-14 standard) from −0.27 ± 0.09‰ to +0.21 ± 0.08‰. Samples deposited in a mainly limnic environment with oxygenated bottom water have a mean δ⁵⁶Fe of +0.08 ± 0.13‰, which is identical to the mean Fe isotopic composition of igneous rocks and oxic marine sediments. In contrast, sediments that formed in brackish water under periodically euxinic conditions display significantly lighter Fe isotope signatures with a mean δ⁵⁶Fe of −0.14 ± 0.19‰. Negative correlations of the δ⁵⁶Fe values with the Fe/Al ratio and S content of the samples suggest that the isotopically light Fe in the periodically euxinic samples is associated with reactive Fe enrichments and sulfides. This is supported by analyses of pyrite separates from this unit that have a mean Fe isotopic composition of −1.06 ± 0.20‰ for δ⁵⁶Fe. The supply of additional Fe with a light Fe isotopic signature can be explained with the shelf to basin Fe shuttle model. According to the Fe shuttle model, oxides and benthic ferrous Fe that is derived from dissimilatory iron reduction from shelves is transported and accumulated in euxinic basins. The data furthermore suggest that the euxinic water has a negative dissolved δ⁵⁶Fe value of about −1.4‰ to −0.9‰. If negative Fe isotopic signatures are characteristic for euxinic sediment formation, widespread euxinia in the past might have shifted the Fe isotopic composition of dissolved Fe in the ocean towards more positive δ⁵⁶Fe values.     

Fe Isotope Compositions of Cyprus Umbers

Submarine metalliferous sedimentary rocks are chemical precipitates resulted from hydrothermal exhalation near mid‐ocean ridge or faults. They record the submarine hydrothermal activity between lithosphere and hydrosphere and are critical for understanding Fe cycling in marine environment. Fe was expelled from the hydrothermal vent systems and was oxidized and precipitated in the ambient seawater, where the precipitation of hydrothermal Fe is largely controlled by oxidation state of seawater and is potentially revealed by its Fe isotope compositions. This hydrothermal process in modern hydrothermal vent systems have been well observed, but that for the ancient ones are still not well known. Umbers, or ferromanganoan sediments, overlying Troodos ophiolite in Cyprus of Mid‐Cretaceous age thus provides an excellent example for understanding the Fe cycles in ancient submarine hydrothermal process. Samples were collected from Margi village in Troodos and are mostly amorphous Fe‐Mn oxy‐hydroxides with very minor quartz, goethite, smectite and silicates such as clinopyroxene derived from the volcanic rocks. There is no terrestrial, detrital component. Samples were analyzed for their whole‐rock element and Fe isotope compositions. The results show that samples are composed mainly of SiO₂ (13～80 wt%), Fe₂O₃ (9～54 wt%) and MnO (1.5～10.4 wt%), with minor Al₂O₃ (0.7～4.3 wt%). PAAS‐normalized REE patterns are near flat with significantly negative Ce anomalies (Ce/Ce* is from 0.2 to 0.5) and slightly positive Eu anomalies (Eu/Eu* is around 1.1), indicating a source from the oxidized seawater and the high‐temperature hydrothermal fluids. δ⁵⁶FeIRMM‐014 values of samples are ‐0.32‰ to ‐0.15‰, with an average of ‐0.20‰, which are consistent with those of the hydrothermal fluids previously reported. The narrow Fe isotope compositions of Cyprus umbers that are close to those of submarine hydrothermal fluids indicates near complete oxidation of hydrothermal Fe²⁺ during its expulsion from the hydrothermal vent.     

Spatially controlled Fe and Si isotope variations: an alternative view on the formation of the Torres del Paine pluton

We present new Fe and Si isotope ratio data for the Torres del Paine igneous complex in southern Chile. The multi-composition pluton consists of an approximately 1 km vertical exposure of homogenous granite overlying a contemporaneous 250-m-thick mafic gabbro suite. This first-of-its-kind spatially dependent Fe and Si isotope investigation of a convergent margin-related pluton aims to understand the nature of granite and silicic igneous rock formation. Results collected by MC-ICP-MS show a trend of increasing δ⁵⁶Fe and δ³⁰Si with increasing silica content as well as a systematic increase in δ⁵⁶Fe away from the mafic base of the pluton. The marginal Torres del Paine granites have heavier Fe isotope signatures (δ⁵⁶Fe = +0.25 ± 0.02 2se) compared to granites found in the interior pluton (δ⁵⁶Fe = +0.17 ± 0.02 2se). Cerro Toro country rock values are isotopically light in both Fe and Si isotopic systems (δ⁵⁶Fe = +0.05 ± 0.02 ‰; δ³⁰Si = ?0.38 ± 0.07 ‰). The variations in the Fe and Si isotopic data cannot be accounted for by local assimilation of the wall rocks, in situ fractional crystallization, late-stage fluid exsolution or some combination of these processes. Instead, we conclude that thermal diffusion or source magma variation is the most likely process producing Fe isotope ratio variations in the Torres del Paine pluton.     

Iron Isotopic Compositions of Geological Reference Materials and Chondrites

High‐precision iron isotopic compositions for Fe‐bearing geological reference materials and chondrites with a wide range of matrices (e.g., silicates, oxides, organic‐bearing materials) are reported. This comprehensive data set should serve as a reference for iron isotopic studies across a range of geological and biological disciplines for both quality assurance and inter‐laboratory calibration. Where comparison is available, the iron isotopic compositions of most geological reference materials measured in this study were in agreement with previously published data within quoted uncertainties. Recommendations for the reporting of future iron isotopic data and associated uncertainties are also presented. Long‐term repeat analyses of all samples indicate that highly reproducible iron isotopic measurements are now obtainable (± 0.03‰ and ± 0.05‰ for δ⁵⁶Fe and δ⁵⁷Fe, respectively).     

Micro-scale sulfur isotope and chemical variations in sphalerite from the Bleiberg Pb-Zn deposit,Eastern Alps,Austria

The Bleiberg Pb-Zn deposit in the Drau Range is the type locality of Alpine-type carbonate-hosted Pb-Zn deposits. Its origin has been the subject of on-going controversy with two contrasting genetic models proposed: (1) the SEDEX model, with ore forming contemporaneously with sedimentation of the Triassic host rocks at about 220 Ma vs. (2) the epigenetic MVT model, with ores forming after host rock sedimentation at about 200 Ma or later. Both models assume that, on a deposit or even district scale, a fixed paragenetic sequence of ore minerals can be established. The results of our detailed petrographic, chemical and sulfur isotope study of two key ore-samples from two major ore horizons in the Wetterstein Formation at Bleiberg (EHK02 Erzkalk horizon and Blb17 Maxer Bänke horizon) demonstrate that there is no fixed paragenetic sequence of ore minerals. Small-scale non-systematic variations are recorded in textures, sphalerite chemistry and δ³⁴S. In each sample, texturally different sphalerite types (colloform schalenblende, fine- and coarse-grained crystalline sphalerite) co-occur on a millimeter to centimeter scale. These sphalerites represent multiple mineralization stages/pulses since they differ in their trace element inventory and in their δ³⁴S. Nonetheless, there is some correspondence of sphalerite micro-textures, sulfur isotope and chemical composition between the two samples, with microcrystalline colloform schalenblende being Fe-rich, having high Fe/Cd (15 and 9, respectively) and a light sulfur isotope composition (δ³⁴S −26.0 to −16.2‰). Cadmium-rich and Fe-poor sphalerite in both samples has relatively heavier sulfur isotope composition: in sample EHK02 this sphalerite has Fe/Cd of ∼0.5 and δ³⁴S from −6.6 to −4.6‰; in sample Blb17 Fe/Cd is ∼0.1 and δ³⁴S ranges from −15.0 to −1.5‰. Barite, which is restricted to sample EHK02, has δ³⁴S ≈ 17‰. The large variations in δ³⁴S recorded on the mm to cm-scale is consistent with variable contributions of reduced sulfur from two different sulfur reservoirs. The dominant reservoir with δ³⁴S values <−20‰ likely results from local bacteriogenic sulfate reduction (BSR), whereas the second reservoir, with δ³⁴S about −5‰ suggests a hydrothermal source likely linked with thermochemical sulfate reduction (TSR). Based on this small- to micro-scale study, no simple, deposit-wide paragenetic and sulfur isotope evolution with time can be established. In the Erzkalk ore (sample EHK02) an earlier Pb-Zn-Ba stage, characterized by heavy sulfur isotope values, is succeeded by a light δ³⁴S-dominated Zn-Pb-F stage. In contrast, the several mineralization pulses identified in the stratiform Zn-Pb-F Maxer Bänke ore (sample Blb17) define a broad trend to heavier sulfur isotope values with time. The interaction documented in these samples between two sulfur reservoirs is considered a key mechanism of ore formation.     

Variation of copper isotopes in chalcopyrite from Dabu porphyry Cu-Mo deposit in Tibet and implications for mineral exploration

The study presents copper (Cu) isotope data of mineral separates of chalcopyrite from four drill core samples in the Miocene Dabu porphyry Cu-Mo deposit formed in a post-collisional setting in the Gangdese porphyry copper belt, southern Tibet. Copper isotope values in hypogene chalcopyrite range from –1.48‰ to +1.12‰, displaying a large variation of up to 2.60‰, which demonstrates Cu isotope fractionation at high-temperature during hydrothermal evolution. The majority of measured chalcopyrite isotopic compositions show a gradual increasing trend from –1.48‰ to +1.12‰ with the increase of drilling depth from 130m to 483m, as the alteration assemblages change from potassic to phyllic. Similarly, the other δ⁶⁵Cu values (δ⁶⁵Cu = ((⁶⁵Cu/⁶³Cu)_sample/(⁶⁵Cu/⁶³Cu)_standard − 1) × 1000) of the chalcopyrite show a gradual increasing trend from −1.48‰ to +0.59‰ with the decrease of drilling depth from 130 m to 57 m, as the alteration assemblages change from potassic, phyllic, through argillic to relatively fresh. These observations suggest a genetic link between Cu isotope variation and silicate alteration assemblages formed at different temperatures, indicative of a Rayleigh precipitation process resulting in the large variation of δ⁶⁵Cu values at Dabu. In general, samples closest to the center of hydrothermal system dominated by high-temperature potassic alteration are isotopically lighter, whereas samples dominated by low-temperature phyllic alteration peripheral to the center are isotopically heavier. The predicted flow pathways of hydrothermal fluids are from No. 0 to No. 3 exploration line, and the lightest δ⁶⁵Cu values are the most proximal to the hydrothermal source. Finally, we propose that the northwest side of the No. 0 exploration line has high potential for hosting undiscovered orebodies. The pattern of Cu isotope variation in conjunction with the features of silicate alteration in porphyry system can be used to trace the hydrothermal flow direction and to guide mineral exploration.     

Iron isotope systematics in estuaries: The case of North River, Massachusetts (USA)

Recent studies have suggested that rivers may present an isotopically light Fe source to the oceans. Since the input of dissolved iron from river water is generally controlled by flocculation processes that occur during estuarine mixing, it is important to investigate potential fractionation of Fe-isotopes during this process. In this study, we investigate the influence of the flocculation of Fe-rich colloids on the iron isotope composition of pristine estuarine waters and suspended particles. The samples were collected along a salinity gradient from the fresh water to the ocean in the North River estuary (MA, USA). Estuarine samples were filtered at 0.22 μm and the iron isotope composition of the two fractions (dissolved and particles) were analyzed using high-resolution MC-ICP-MS after chemical purification. Dissolved iron results show positive δ⁵⁶Fe values (with an average of 0.43 ± 0.04‰) relative to the IRMM-14 standard and do not display any relationships with salinity or with percentage of colloid flocculation. The iron isotopic composition of the particles suspended in fresh water is characterized by more negative δ⁵⁶Fe values than for dissolved Fe and correlate with the percentage of Fe flocculation. Particulate δ⁵⁶Fe values vary from −0.09‰ at no flocculation to ∼0.1‰ at the flocculation maximum, which reflect mixing effects between river-borne particles, lithogenic particles derived from coastal seawaters and newly precipitated colloids. Since the process of flocculation produces minimal Fe-isotope fractionation in the dissolved Fe pool, we suggest that the pristine iron isotope composition of fresh water is preserved during estuarine mixing and that the value of the global riverine source into the ocean can be identified from the fresh water values. However, this study also suggests that δ⁵⁶Fe composition of rivers can also be characterized by more positive δ⁵⁶Fe values (up to 0.3‰) relative to the crust than previously reported. In order to improve our current understanding of the oceanic iron isotope cycling, further work is now required to determine the processes controlling the fractionation of Fe-isotopes during continental run-off.     

Copper and iron isotope fractionation in mine tailings at the Laver and Kristineberg mines,northern Sweden

Previous research has shown that Cu and Fe isotopes are fractionated by dissolution and precipitation reactions driven by changing redox conditions. In this study, Cu isotope composition (⁶⁵Cu/⁶³Cu ratios) was studied in profiles through sulphide-bearing tailings at the former Cu mine at Laver and in a pilot-scale test cell at the Kristineberg mine, both in northern Sweden. The profile at Kristineberg was also analysed for Fe isotope composition (⁵⁶Fe/⁵⁴Fe ratios). At both sites sulphide oxidation resulted in an enrichment of the lighter Cu isotope in the oxidised zone of the tailings compared to the original isotope ratio, probably due to preferential losses of the heavier Cu isotope into the liquid phase during oxidation of sulphides. In a zone with secondary enrichment of Cu, located just below the oxidation front at Laver, δ⁶⁵Cu (compared to ERM-AE633) was as low as −4.35 ± 0.02‰, which can be compared to the original value of 1.31 ± 0.03‰ in the unoxidised tailings. Precipitation of covellite in the secondary Cu enrichment zone explains this fractionation. The Fe isotopic composition in the Kristineberg profile is similar in the oxidised zone and in the unoxidised zone, with average δ⁵⁶Fe values (relative to the IRMM-014) of −0.58 ± 0.06‰ and −0.49 ± 0.05‰, respectively. At the well-defined oxidation front, δ⁵⁶Fe was less negative, −0.24 ± 0.01‰. Processes such as Fe(II)–Fe(III) equilibrium and precipitation of Fe-(oxy)hydroxides at the oxidation front are assumed to cause this Fe isotope fractionation. This field study provides additional support for the importance of redox processes for the isotopic composition of Cu and Fe in natural systems.