Fe Isotope Compositions Research Articles

Early diagenesis of anthropogenic uranium in lakes receiving deep groundwater from the Kiruna mine, northern Sweden

The uranium (U) concentrations and isotopic composition of waters and sediment cores were used to investigate the transport and accumulation of U in a water system (tailings pond, two lakes, and the Kalix River) receiving mine waters from the Kiruna mine. Concentrations of dissolved U decrease two orders of magnitude between the inflow of mine waters and in the Kalix River, while the concentration of the element bound to particulate matter increases, most likely due to sorption on iron‑manganese hydroxides and organic matter. The vertical distribution of U in the water column differs between two polluted lakes with a potential indication of dissolved U supply from sediment's pore waters at anoxic conditions. Since the beginning of exposure in the 1950s, U concentrations in lake sediments have increased >20-fold, reaching concentrations above 50 μg g-1. The distribution of anthropogenic U between the lakes does not follow the distribution of other mine water contaminants, with a higher relative proportion of U accumulating in the sediments of the second lake.Concentrations of redox-sensitive elements in the sediment core as well as Fe isotopic composition were used to re-construct past redox-conditions potentially controlling early diagenesis of U in surface sediments. Two analytical techniques (ICP-SFMS and MC-ICP-MS) were used for the determination of U isotopic composition, providing an extra dimension in the understanding of processes in the system. The (234 U)/(238 U) activity ratio (AR) is rather uniform in the tailings pond but varies considerably in water and lake sediments providing a potential tracer for U transport from the Kiruna mine through the water system, and U immobilization in sediments. The U mass balance in the Rakkurijoki system as well as the amount of anthropogenic U accumulated in lake sediments were evaluated, indicating the immobilization in the two lakes of 170 kg and 285 kg U, respectively.

Variation of Cu, Fe, S and Pb isotopes in sulfides from hydrothermal mineralization from the Yenice region in Çanakkale, Biga Peninsula, NW Turkey

We report the iron (n = 13), copper (n = 13), sulfur (n = 25) and lead (n = 31) isotope compositions of mineralized samples from porphyry, skarn and epithermal mineralization in the Yenice region that lies in the east of the Biga Peninsula, Turkey. The vast majority of isotopic data were analyzed from the world-class Arapuçandere Pb-Zn-Cu (Ag-Au) deposit that is one of the best example of intermediate sulfidation epithermal deposits within the Serbo-Macedonian-Rhodope metallogenic belt in the northeastern of the Aegean. The δ56Fe values range from −1.06 to + 0.46‰ and reflect the complex interplay between redox, Rayleigh and kinetic effects. The δ65Cu values also define a narrow ranges of −0.07 to +0.77‰ that is typical of primary minerals in magmatic-hydrothermal ore deposits worldwide. The Cu isotope values of chalcopyrite from the Arapuçandere deposit tend to progressively increase through the surface, which creates a vector from the proximal to distal portions of magmatic-hydrothermal environment, possibly with local supergene processes within deposit. The sulfides from the Yenice region have a relatively narrow range of δ34S values that range between −4.0 and 3.9‰ and mostly cluster around 0‰, indicating sulfur is mainly derived from a magmatic source at the time of mineralization. All the Pb isotope data that includes results from ore minerals fall within the fields defined by Oligocene to Miocene Aegean-West Anatolian magmatic rocks. This observation supports the hypothesis that the metals and sulfur contained within all the various styles of mineralization considered here were derived entirely from these granitoids, with no significant contamination from the local basement rocks. This observation also constrains the processes controlling the Fe and Cu isotope compositions to those operating within the porphyry, skarn, and epithermal hydrothermal systems, rather than contamination by interaction with the basement rocks.

Iron isotope and trace metal variations during mantle metasomatism: In situ study on sulfide minerals from peridotite xenoliths from Nógrád-Gömör Volcanic Field (Northern Pannonian Basin)

Sulfides from lherzolite and wehrlite xenoliths from the Nógrád-Gömör Volcanic Field (NGVF), located in the Northern Pannonian Basin, were studied to understand the behavior of chalcophile and siderophile elements during mafic melt – peridotite interaction. We applied in situ methods to analyze the major and trace elements, as well as Fe isotope compositions of sulfide minerals. Sulfides are more abundant in wehrlites (~0.03 vol%) and are often enclosed in silicates, whereas in lherzolites, they are scarcer (~0.01 vol%) and predominantly interstitial. Monosulfide solid solution and pentlandite are the most common sulfide phases in the lherzolite xenoliths, whereas in wehrlite xenoliths it is pyrrhotite and chalcopyrite. Consequently, wehrlitic sulfides show higher bulk Fe and Cu but lower bulk Ni and Co contents compared to the lherzolitic sulfides. Trace elements with both chalcophile and siderophile character (Ge, Se, Te, and Re) show lower, whereas highly chalcophile elements (Zn, Cd, Sb, and Tl) show higher concentrations in wehrlitic sulfides compared to lherzolitic ones. Highly siderophile elements show no systematic difference between the sulfides of the two xenolith series, which suggests moderate enrichment in these elements in wehrlite bulk rocks due to their higher sulfide content. Sulfide δ56Fe signature indicates variable isotopic composition both in lherzolites (δ56Fe: −0.13 to +0.56‰) and wehrlites (δ56Fe: −0.20 to +0.84‰) relative to the terrestrial mantle (δ56Fe: +0.025 ± 0.025‰; Craddock et al., 2013). However, irrespectively of the xenolith lithology, there is a significant difference between the δ56Fe of sulfides from the two sampling localities: NTB /North/: vary from −0.20 to +0.04‰ and NME /South/: vary from +0.56 to +0.84‰. This suggests that the Fe isotopic ratios of sulfides are not modified by the wehrlitization process. Difference in sulfide δ56Fe between the two xenolith localities is probably because of the higher, isotopically heavier (δ56Fe: from +1.28 to +1.60‰; Ciążela et al., 2019) chalcopyrite content in sulfides from the NME xenoliths compared to those from the NTB xenoliths irrespectively to their lithology. Our results also indicate sulfide and chalcophile element enrichment resulting from metasomatism in the subcontinental lithospheric mantle. We suggest that this process affected the regional metal distribution and has implications for global metal mass balance within the subcontinental lithosphere.

Iron isotope constraints on the metal source and depositional environment of the Neoproterozoic banded iron- and manganese deposits in Urucum, Brazil

The Urucum area of Brazil hosts a series of Cryogenian ironstones intercalated by oxide-dominated manganese layers. The Urucum iron and manganese formations (IF-MnF) are among the largest sedimentary iron and associated manganese deposits of the Neoproterozoic, however, the depositional model and the source of metals for the IF-MnF in this area are highly controversial. In this study, we performed systematic Fe isotope analysis on fresh and geochemically characterized drill core samples of the Urucum iron and manganese formation deposited in the center of the ancient Urucum graben system. The samples have a large variation in Fe isotope composition, with a δ56Fe range of −2.04‰ to +0.75‰, and exhibit a general trend of decreasing δ56Fe values with increasing manganese contents. The low δ56Fe values of the IF and MnF samples reflect Rayleigh fractionation processes of contineous partial oxidation of aqueous Fe(II) prior to deposition at the sampling site. Using a mixing model and previously published Nd isotope data on the same samples, we estimated that benthic (i.e., porewaters released from submarine sediments in the Urucum basin) Fe fluxes provided 7–50% of total Fe in the Urucum IF-MnF, and the rest of Fe source was from low-temperature hydrothermal vents. Based on combined Fe and Nd isotope data of the Urucum IF-MnF, we propose that low-temperature hydrothermal fluids and benthic fluxes of pore waters were mixed and transported by an upwelling current. The fluid subsequently experienced partial oxidation during the transportation process and became enriched in light Fe isotopes. In the Urucum graben basin, the iron- and manganese-rich oxides deposition occurred progressively under increasingly oxidizing conditions, and such process could have operated repeatedly to produce the alternation of iron and manganese formations. The chemical sediments of the Urucum IF-MnF deposits thus reflect the existence of a sharp redox gradient in the marine environment during the late Cryogenian period.

New insight into iron biogeochemical cycling in soil-rice plant system using iron isotope fractionation

Iron (Fe) migration in soil-plants is a critical part of Fe biogeochemical cycling in the earth surface system. Fe isotope fractionation analysis in the soil-rice system is promising for quantitatively assessing various pathways and clarifying Fe transformation processes. However, the mechanisms of Fe isotope fractionation in the soil-rice system are not well understood. In this study, the Fe isotopic compositions (δ56Fe) of rhizosphere soils, pore water, Fe plaque, and rice plant tissues at the jointing and mature stages of the plants were determined. The rice plants were slightly enriched in heavier δ56Fe by ∼0.3‰ relative to the soil, and the stele and cortex showed similar δ56Fe values, indicating that the uptake of Fe by rice plants predominantly occurred via Fe(III)-phytosiderophores (Fe(III)-PS) chelation, but not Fe(III) reduction. Additionally, at both the jointing and mature stages, the rice plant tissues showed similar δ56Fe values. However, the Fe isotope fractionation between the roots and stems (Δ56Feroot−stem) was 1.39 ± 0.13‰, which is similar to the previously Ab initio-calculated values between Fe(III)-citrate and Fe(III)- 2-deoxymugineic acid (DMA), indicating that both the phloem and xylem have similar δ56Fe values, and the major Fe-chelating substances in the phloem of the rice plants are Fe(III)-DMA and Fe(II)- Nicotianamine (NA). Therefore, this study demonstrates that Fe isotope fractionation can be used as a signature for interpreting the Fe uptake and translocation mechanism in the soil-rice system.

Iron Isotope Compositions of Coexisting Sulfide and Silicate Minerals in Sudbury-Type Ores from the Jinchuan Ni-Cu Sulfide Deposit: A Perspective on Possible Core-Mantle Iron Isotope Fractionation

Many studies have shown that the average iron (Fe) isotope compositions of mantle-derived rocks, mantle peridotite and model mantle are close to those of chondrites. Therefore, it is considered that chondrite values represent the bulk Earth Fe isotope composition. However, this is a brave assumption because nearly 90% of Fe of the Earth is in the core, where its Fe isotope composition is unknown, but it is required to construct bulk Earth Fe isotope composition. We approach the problem by assuming that the Earth’s core separation can be approximated in terms of the Sudbury-type Ni-Cu sulfide mineralization, where sulfide-saturated mafic magmas segregate into immiscible sulfide liquid and silicate liquid. Their density/buoyancy controlled stratification and solidification produced net-textured ores above massive ores and below disseminated ores. The coexisting sulfide minerals (pyrrhotite (Po) > pentlandite (Pn) > chalcopyrite (Cp)) and silicate minerals (olivine (Ol) > orthopyroxene (Opx) > clinopyroxene (Cpx)) are expected to hold messages on Fe isotope fractionation between the two liquids before their solidification. We studied the net-textured ores of the Sudbury-type Jinchuan Ni-Cu sulfide deposit. The sulfide minerals show varying δ56Fe values (−1.37–−0.74‰ (Po) < 0.09–0.56‰ (Cp) < 0.53–1.05‰ (Pn)), but silicate minerals (Ol, Opx, and Cpx) have δ56Fe values close to chondrites (δ56Fe = −0.01 ± 0.01‰). The heavy δ56Fe value (0.52–0.60‰) of serpentines may reflect Fe isotopes exchange with the coexisting pyrrhotite with light δ56Fe. We obtained an equilibrium fractionation factor of Δ56Fesilicate-sulfide ≈ 0.51‰ between reconstructed silicate liquid (δ56Fe ≈ 0.21‰) and sulfide liquid (δ56Fe ≈ −0.30‰), or Δ56Fesilicate-sulfide ≈ 0.36‰ between the weighted mean bulk-silicate minerals (δ56Fe[0.70ol,0.25opx,0.05cpx] = 0.06‰) with weighted mean bulk-sulfide minerals (δ56Fe ≈ −0.30‰). Our study indicates that significant Fe isotope fractionation does take place between silicate and sulfide liquids during the Sudbury-type sulfide mineralization. We hypothesize that significant iron isotope fractionation must have taken place during core–mantle segregation, and the bulk Earth may have lighter Fe isotope composition than chondrites although Fe isotope analysis on experimental sulfide-silicate liquids produced under the varying mantle depth conditions is needed to test our results. We advocate the importance of further research on the subject. Given the close Fe-Ni association in the magmatic mineralization and the majority of the Earth’s Ni is also in the core, we infer that Ni isotope fractionation must also have taken place during the core separation that needs attention.

Iron isotope fractionation during sulfide liquid evolution in Cu–PGE mineralization of the Eastern Gabbro, Coldwell Complex, Canada

In spite of the fact that metal stable isotopes are not expected to exhibit large equilibrium fractionations at magmatic temperatures, Fe isotope compositions of base-metal sulfides are increasingly being used to characterize the processes that generate and modify Ni–Cu–platinum-group element (PGE) deposits. In the Eastern Gabbro of the Coldwell Complex, Canada, the δ56Fe values (relative to IRMM-014) of pyrrhotite (−1.48‰ to −0.16‰) are consistently negative and exhibit no correlation with style of mineralization, whereas δ56Fe values of chalcopyrite (−0.65‰ to 1.11‰) are largely positive (except for the W Horizon) and decreases in samples from Footwall Zone, through the Main Zone ≈ Four Dams ≈ Sally, to the W Horizon. Source heterogeneity, sulfide segregation, variations in R factor, crustal contamination, hydrothermal fluids, and redox reactions have been ruled out as having had a significant effect on the Fe isotope composition of both pyrrhotite and chalcopyrite. Rather, the positive correlation between δ56FeCcp and the pyrrhotite/chalcopyrite ratio of the mineralized zones indicates that the large range in δ56FeCcp is likely due to variations in the amount of monosulfide solid solution (MSS) that crystallized before intermediate solid solution (ISS). Monosulfide solid solution favors 54Fe, thus the δ56Fe of the residual Cu-rich liquid would be higher than the initial sulfide liquid and variable depending on how much MSS crystallized before ISS. Subsequent to the solidification of MSS, it exsolved pyrrhotite with minor pentlandite, with troilite exsolving from pyrrhotite at lower temperatures. The large range in δ56FePo is likely due to the partitioning of 54Fe and 56Fe among these phases and the variability in the proportion of the phases in the samples. These conclusions have important implications for the applicability of Fe isotopes in base-metal sulfides to characterizing magmatic Ni–Cu–PGE systems as the Fe isotope composition of two of the most dominant base-metal sulfides in these systems, pyrrhotite and chalcopyrite, are not controlled by mineralizing processes, but rather subsolidus processes.

Iron, copper, and zinc isotopic fractionation in seafloor basalts and hydrothermal sulfides

Studies of the Fe, Cu, and Zn isotopic compositions of volcanic rocks and sulfides provide an important tool for understanding magmatic, hydrothermal, and alteration processes, thereby enabling the determination of both transition metal sources and the quantification of the petrologic environmental impacts of hydrothermal activities. In this study, the δ56Fe and δ57Fe values of the mid-ocean ridge basalts (MORBs) are higher than those of the seafloor hydrothermal fluids, while the reverse is true for the δ66Zn and δ68Zn values, suggesting that basalt-fluid interactions preferentially incorporate isotopically light Fe and heavy Zn into the fluids, resulting in the relative enrichment of heavier Fe and lighter Zn isotopes in altered basaltic rocks. Most of the δ56Fe values (−1.96 to +0.11‰) of the sulfide minerals are within the range of the vent fluids, but they are significantly lower than those of the MORBs and back-arc basin basalts (BABBs), suggesting that the Fe in the sulfides was mainly derived from the fluids. However, the majority of the chalcopyrite δ56Fe and δ57Fe values are higher than those of the sphalerite and pyrite. This suggests that high-temperature sulfide minerals are enriched in 56Fe and 57Fe, whereas medium- and low-temperature sulfides are depleted in 56Fe and 57Fe. Moreover, the δ65Cu (−0.88 to −0.16‰) and δ66Zn (−0.39 to −0.03‰) values of the sulfide minerals are significantly lower than those of the MORBs, BABBs, and fluids, suggesting that 63Cu and 64Zn were preferentially removed from the fluids and incorporated into the chalcopyrite and sphalerite, respectively. Consequently, vent fluid injection and deposition can cause the heavier Cu and Zn isotopic compositions of hydrothermal plumes, seawater, and sediments.

Iron and magnesium isotope systematics from the Shuangwang gold deposit in the Qinling Orogen, central China

Iron and Magnesium isotopes have been increasingly widely applied to trace mineralization processes of hydrothermal ore systems. In this study, Fe and Mg isotope compositions of whole-rocks, Fe-bearing minerals (pyrite and ankerite) and Mg-bearing mineral (ankerite) from the Shuangwang gold deposits are investigated to evaluate Fe and Mg isotope behaviors in a gold deposit hydrothermal system and provide new constraints on ore-forming processes. The results showed that the magmatic rocks in the Shuangwang gold deposit (mainly granodiorite, monzonitic granite and lamprophyre) yielded δ56Fe values of 0.05–0.10‰ and δ26Mg values concentrated in a narrow range from −0.23‰ to −0.21‰. The gold orebodies are hosted by a NW-trending breccia belt. The wall rock samples (mainly argillaceous limestone, carbonaceous slate and albitite) have higher δ56Fe values of 0.12–0.29‰ and a wide δ26Mg range from −2.54‰ to −0.35‰. Pyrite mineral separates show larger δ56Fe variation from −0.44‰ to 0.16‰, whereas ankerite has a small δ56Fe range from −0.15‰ to −0.06 and a δ26Mg range from −0.66‰ to −0.35‰.

Iron isotopes trace primordial magma ocean cumulates melting in Earth's upper mantle.

The differentiation of Earth ~4.5 billion years (Ga) ago is believed to have culminated in magma ocean crystallization, crystal-liquid separation, and the formation of mineralogically distinct mantle reservoirs. However, the magma ocean model remains difficult to validate because of the scarcity of geochemical tracers of lower mantle mineralogy. The Fe isotope compositions (δ57Fe) of ancient mafic rocks can be used to reconstruct the mineralogy of their mantle source regions. We present Fe isotope data for 3.7-Ga metabasalts from the Isua Supracrustal Belt (Greenland). The δ57Fe signatures of these samples extend to values elevated relative to modern equivalents and define strong correlations with fluid-immobile trace elements and tungsten isotope anomalies (μ182W). Phase equilibria models demonstrate that these features can be explained by melting of a magma ocean cumulate component in the upper mantle. Similar processes may operate today, as evidenced by the δ57Fe and μ182W heterogeneity of modern oceanic basalts.

Iron isotope constraints on the genesis of magnetite ore in the Huogeqi deposit of Inner Mongolia autonomous region in northern China

The Huogeqi deposit is a major Cu–Fe–Pb–Zn deposit in China. Numerous studies have been conducted on the genesis of Cu–Pb–Zn sulfides of this deposit; but detailed researches on the genesis of magnetite ore bodies and its relationship to sulfide ores are few. This study utilizes field and microscopic techniques to showcase the hydrothermal characteristics of magnetite ore and tremolite rocks, including net-veined magnetite ore, which cuts across carbonate rock and quartzite, and intrusive contacts between magnetite-bearing tremolite rocks and quartzite, carbonaceous slate, and carbonate rock. Furthermore, calcite with metasomatic relict texture could be widely observed near magnetite and tremolite. Magnetite-bearing tremolite rocks with low contents of trace elements, rare earth elements, and obvious positive anomalies of Eu differed from the mica schist and carbonaceous slate, but were consistent with the carbonate rocks, revealing that the magnetite ore and tremolite rocks have a hydrothermal origin and are closely related to carbonate rocks. The Fe isotopic compositions of 22 magnetite and 17 wall samples were determined using MC-ICP-MS methods. δ56Fe values of magnetite-bearing tremolite rocks varied from −0.57 to −0.15‰ (average, −0.38‰), which differed from those of the mica schist (0.27–0.33‰), quartzite (−0.12 to 0.57‰), and carbonaceous slate (0.30–0.38‰), but were similar to the carbonate rocks (−0.38 to −0.51‰). δ56Fe values of magnetite varied from −0.48 to 0.36‰ (average, −0.11‰), which differed from banded-iron formation and magmatic magnetite deposits but were like skarn deposits. The δ56Fe value of the initial ore-forming fluid was −0.09‰ at 350 °C, which is consistent with the fluid that likely originated from the fluid exsolution of granite. According to theoretical calculations, δ56Fe values of the residual fluid after precipitation of magnetite ores ranged from −1.01 to −0.94‰, and that for pyrite precipitation ranged from −0.02 to 0.07‰, which is consistent with the measured Fe isotopic data of pyrite. Hence, we suggest that the hydrothermal magnetite and Cu–Pb–Zn sulfides of the Huogeqi skarn deposit could be derived from similar hydrothermal fluids.

Iron isotope fractionation in reduced hydrothermal gold deposits: A case study of the Wulong gold deposit, Liaodong Peninsula, East China

Abstract Iron isotope fractionation in hydrothermal systems is a useful diagnostic tool for tracing ore-forming processes. Here, we report on the Fe isotopic compositions of a suite of hydrothermal minerals from ores (pyrite, pyrrhotite, and quartz) from the Wulong gold deposit, Liaodong Peninsula, East China. Pyrites from quartz sulfide ores show a δ56Fe (56Fe/54Fe in the sample relative to IRMM-14) range from +0.11 ± 0.03‰ to +0.78 ± 0.03‰ (2SD), and pyrrhotites from the same vein are isotopically lighter than the pyrites, varying between −0.85 ± 0.01‰ and −0.07 ± 0.00‰. This result is consistent with theoretical predictions of equilibrium fractionation and published mineral compositions. For the first time, to our knowledge, we report the Fe isotopes of hydrothermal quartz that records the isotopic compositions of the ore-forming fluids. Two quartz separates in the quartz-sulfide vein yield δ56Fe values of −0.02 ± 0.02‰ and +0.07 ± 0.07‰. Our Fe isotope fractionation calculations show that pyrrhotite with light Fe isotopes crystallized first from the ore-forming fluids, which indicates a relatively reduced condition for the initial ore-forming fluids. Then the remaining fluids with heavy Fe isotopes precipitated pyrites with positive δ56Fe values, and their mineral crystallization sequence records an increase of oxygen fugacity during mineralization. Gold deposits in Wulong and Jiaodong share many similar geological characteristics. The pyrites from the Wulong deposit have higher δ34S values (+0.5 to +4.1‰) than the pyrrhotites (–1.2 to +1.2‰). Pyrites from the Jiaodong gold deposits show a wide range of both positive and negative δ56Fe values as well as high δ34S values, whereas those from the Wulong deposit have a relatively narrow range of positive δ56Fe values and near-zero δ34S values. The differences in Fe isotopes may be due to early precipitation of pyrrhotite with light Fe isotopes under a relatively low oxygen fugacity environment in the Wulong deposit, resulting in pyrite precipitated from the remaining fluids with heavy isotopes. The sulfur isotope variations between Wulong and Jiaodong gold deposits reflect differences in their source regions rather than oxygen fugacities. In addition, we have compiled Fe isotopic compositions of pyrites and pyrrhotites from different types of ore deposits to investigate their Fe isotopic behavior in magmatic-hydrothermal systems. Pyrite grains show a wide range of δ56Fe values. Positive pyrite δ 56Fe values reflect an equilibrium isotope effect, whereas negative pyrite δ56Fe values may be due to kinetic isotope effects or to a mixture of sedimentary host rocks. Pyrrhotite grains show similar negative δ56Fe values, and they have a strong influence on the Fe isotope systematics in magmatic and hydrothermal systems. Our data show that Fe isotopes can be used to trace precipitation orders of pyrite and pyrrhotite and oxygen fugacity evolution in relatively reduced hydrothermal deposits.

Coupled stable chromium and iron isotopic fractionation tracing magmatic mineral crystallization in Archean komatiite-tholeiite suites

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.

When a mid-ocean ridge encroaches a continent: Seafloor-type hydrothermal activity in Lake Asal (Afar Rift)

At the place where the submarine Aden Ridge encroaches on the African continent and interacts with the East African Rift system, two small basins form: Ghoubbet-al-Kharab and Lake Asal. Whereas Ghoubbet-al-Kharab is connected to the open ocean, Lake Asal is a typical example of oceanic “embryo”, which is defined as a system that is detached from the ocean, but has features of a marine basin with an oceanic type crust and a seawater-based water body. In order to shed light on the source of water, type of hydrothermal activity and hydrothermal deposits, and controls on the water chemistry in an oceanic “embryo”, we undertook a mineralogical-geochemical study of the lake water, hydrothermal fluids and hydrothermal carbonate deposits of Lake Asal. The geochemical analyses of lake water and hydrothermal fluids show that Lake Asal (located in an arid zone with strong evaporation and with no riverine input) is fed by seafloor-type hydrothermal fluids according to the following scenario: percolation of seawater along faults and cracks of extension in the rift, reaction of seawater with the hot basaltic rocks and hydrothermal fluid generation, discharge of the hydrothermal fluid in the Asal depression and accumulation of the Lake Asal water body. The fluid venting at the Lake Asal bottom is a mixture of 97% end-member hydrothermal fluid and 3% lake water. The calculated end-member hydrothermal fluid of this oceanic “embryo” is poorer in metals than the seafloor hydrothermal fluids of an open and evolved ocean. In addition to the seawater/rock interaction, the chemistry of Lake Asal is also controlled by evaporation leading to hyper salinity. In a hyper saline water body a number of hydrothermally supplied metals are stabilized as chloride complexes and accumulate. This results in a metal rich and mildly acidic “embryonic” ocean. Unlike an open and evolved modern ocean, the “embryonic” ocean located in an arid zone has heavy C and O isotope composition and light Zn and Fe isotope composition. Calcium isotope compositions of both types of ocean are similarly heavy. There are two genetically different sources of elements to the Lake Asal that are vertically separated: hydrothermal (lower, or bottom) and aeolian (upper, or surficial). Another important control on the lake water chemistry is the formation of carbonate spires at the lake bottom. Ca‑carbonate precipitation immobilizes substantial amount of hydrothermally supplied Ca and drives up the (Mg/Ca)mol of the lake water. Increasing (Mg/Ca)mol of the evolving lake water leads to changes in the mineralogy of spires: from low-Mg calcite to aragonite. Thus, the spire formation exerts a self-control on its mineralogy. Carbonate spire deposition affects also the Ca, Zn and Fe isotope composition of the lake water through adsorption or/and co-precipitation induced isotope fractionation.

Microbial nitrification and acidification of lacustrine sediments deduced from the nature of a sedimentary kaolin deposit in central Japan

Kaolin deposits in the Seto-Tono district, central Japan, were formed by intense kaolinization of lacustrine arkose sediments deposited in small and shallow inland lakes in the late Miocene. Based on mineralogical and stable isotopic (Fe, C, N) studies of Motoyama kaolin deposit in the Seto area, we concluded that it was formed by microbial nitrification and acidification of lacustrine sediments underneath an inland lake. Small amounts of Fe–Ti oxides and Fe-hydroxide in the kaolin clay indicated that iron was oxidized and leached during the kaolinization. The field occurrences indicate that leached ferric iron precipitated on the bottom of the kaolin deposit as limonite crusts, and their significantly fractionated Fe isotope compositions suggest the involvement of microbial activity. The C/N ratios of most of the kaolin clay are distinctly higher than those of modern lacustrine sediment. Although, the possibility of a low-temperature hydrothermal origin of the kaolin deposit cannot be completely ruled out, it is more likely that acidification by dilute nitric acid formed from plant-derived ammonia could have caused the kaolinization, Fe oxidation and leaching. The nitrate-dependent microbial Fe oxidation is consistent with dilute nitric acid being the predominant oxidant.

Does ultrafiltration kinetics bias iron isotope compositions?

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

Fe and S-isotope compositions of hydrothermal deposits from Kings Triple Junction, Lau Basin, southwest Pacific Ocean

We analyzed iron and sulfur isotopic compositions of polymetallic sulfides from an extinct hydrothermal mound near the Kings Triple Junction of the northern Lau basin belonging to a back-arc basin for understanding the origin and mineral zoning processes in this study. Sulfides from the hydrothermal mound's pedestal slab consisting of chalcopyrite and pyrite show enrichment of heavy S-isotope (δ34SV-CDT = +8.3 to +9.6‰). Sphalerite-dominated chimney on the mound's slope also has variable δ34S values between +5.5 and + 8.3‰ from central orifice to outer wall. These isotopic ratios indicate the substantial contribution of heavy isotope rich sulfate-S in seawater circulating within the mound. Low Δ33S values in these sulfides also indicate that the sulfate reduction is of thermal origin, with minimal or no role for microbes. Circulating seawater induced changes in fluid composition and post-depositional zone refinement of certain minerals can explain the variation in δ34S in different layers within the chimney and pedestal slab. The Fe-isotopic compositions (δ56FeIRMM-014) show a range from −1.1 to −0.3‰ in the pedestal slab while they vary between −1.7 and − 0.6‰ at different parts of the peripheral chimney section. We explain such changes are mostly due to redox processes and mineral zoning development during these sulfide deposit formation. The tree-like FeMn oxide growth structures in the vicinity of the hydrothermal mound having a thin birnessite top layer and amorphous iron oxide bottom part show distinct δ56Fe values of −3.0 and − 0.8‰, respectively.

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

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

Discriminate between magmatic- and magmatic-hydrothermal ore deposits using Fe isotopes

Although discriminating high temperature mineral systems, for example, magmatic- vs magmatic-hydrothermal origin Fe deposits, is challenging, the emerging Fe isotope systematics have shown good potentials to provide crucial information on resolving the problem. Here, Fe isotopes of multiple types of samples from one iron oxide-apatite (IOA) deposit and two skarn Fe deposits are measured, aiming to study their behaviors in high temperature magmatic and magmatic-hydrothermal environments. The primary observation of this study is that magnetite samples from high grade ores of magmatic origin IOA deposits has a heavier Fe isotopic signature relative to the associated igneous rocks, whereas a lighter Fe isotopic composition in magnetite samples from magmatic-hydrothermal origin skarn deposits relative to the causative intrusions. Another distinctive feature is that δ56Fe values of the causative intrusions in the magmatic origin IOA deposits are lighter than that of non-fertile intrusions, whereas the ore-associated intrusions of the magmatic-hydrothermal deposit are heavier in δ56Fe than that of non-fertile igneous rocks. The above two observed scenarios suggest that Fe isotope fractionation exists in both magmatic immiscibility and hydrothermal fluid exsolution processes. Magma immiscibility leads to heavy Fe isotope enrichment in immiscible Fe-rich melt phase, and resulting light Fe enrichment in Si-rich melt phase. Hydrothermal fluid exsolution results in lighter Fe isotope enrichment in the exsolved liquid phase, with a heavy Fe isotope enrichment in the residual magma. Fe isotopes behave in different ways in magmatic and magmatic-hydrothermal mineralization processes, which makes Fe isotopes an effective tool to discriminate mineral deposits of magmatic origin from those formed by magmatic-hydrothermal processes.

The Pilot Knob iron ore deposits in southeast Missouri, USA: A high-to-low temperature magmatic-hydrothermal continuum

The Mesoproterozoic St. Francois Mountains igneous terrane in southeast Missouri, USA, contains eight major and several minor IOA/IOCG-type deposits. This study focuses on the Pilot Knob deposits, i.e., the largely massive Pilot Knob Magnetite (PKM) deposit and the Pilot Knob Hematite (PKH) deposit, which is located 240 m stratigraphically above the PKM and consists of variably mineralized bedded hematite and ore hosted in brecciated volcanic agglomerates. The PKM deposit was previously shown to be of magmatic and magmatic-hydrothermal origin, although its formation has not been precisely dated. The origin of the PKH deposit (i.e., sedimentary vs. hydrothermal) and its genetic relationship to the PKM, remain controversial.We present new U-Pb data on apatite intergrown with massive magnetite in the PKM deposit and provide the first precise age for the formation of the PKM ore at 1437.7 ± 5.8 Ma. Petrographic observations of PKH ore, bulk rock compositions, and the mineral chemistry of hematite, which contains up to 2.7% Ti, suggest that the hematite in the PKH deposit crystallized from acidic and hypersaline hydrothermal fluids at a temperature between 200 and 250 °C. The Fe isotopic composition of 9 bedded (δ56Fe = 0.05–0.30‰, average 0.13‰) and 3 brecciated hematite samples (δ56Fe = −0.19 to 0.01‰, average −0.06‰) from the PKH deposit are slightly lighter than the published δ56Fe results of magnetite from the PKM deposit (δ56Fe = 0.06–0.27‰, average 0.17‰). However, all isotopic signatures fall within the magmatic range, indicating that iron in both deposits was originally sourced from a magma. Because of the hydrothermal origin of the PKH deposit, the iron isotopic compositions of the PKM and PKH ores that imply a shared/similar iron source, and the spatial proximity of both deposits, we argue that the PKM and PKH deposits are genetically related and represent two endmembers of a high-to-low temperature magmatic-hydrothermal continuum. In this scenario, ore fluids exsolved from the magma that facilitated the formation of the PKM deposit migrated upwards, infiltrated existing sedimentary structures near the surface, and precipitated hydrothermal hematite ore while preserving the original bedded and brecciated structures.Geochemical signatures of the rhyolites/rhyodacites that host the PKM deposit imply that these rocks are A2-type felsic rocks that were emplaced in a post-collisional extensional setting. Bulk silicate Earth normalized patterns of the PKM deposit and wall rocks display a negative slope from Cs to Lu with negative Nb and Ta anomalies, indicating a hydrous source for the rhyolites and rhyodacites, possibly a subduction-modified subcontinental lithospheric mantle (SCLM). These geochemical signatures support a proposed tectonic setting of the St. Francois Mountains, wherein the igneous terrane developed on a growing continental margin. Episodic mafic-to-intermediate magmatism, and subsequently exsolved hydrothermal fluids, may have formed the cluster of IOA/IOCG-type deposits in the igneous terrane between ~1500 and ~1440 Ma. Within such a context, the PKM and PKH deposits may represent a shallow, small-scale snapshot of processes similar to the ones that form the IOA-IOCG continuum: a deeper magmatic event that exsolved a hydrothermal fluid that forms an overlying ore body.