Deposition Of Iron Formations Research Articles

Living in Their Heyday: Iron-Oxidizing Bacteria Bloomed in Shallow-Marine, Subtidal Environments at ca. 1.88 Ga.

The majority of large iron formations (IFs) were deposited leading up to Earth's great oxidation episode (GOE). Following the GOE, IF deposition decreased for almost 500 Myr. Subsequently, around 1.88 Ga, there was widespread deposition of shallow-water granular iron formations (GIF) within a geologically short time interval, which has been linked to enhanced iron (Fe) supply to seawater from submarine hydrothermal venting associated with the emplacement of large igneous provinces. Previous studies of Fe-rich, microfossil-bearing stromatolites from the ca. 1.88 Ga Gunflint Formation on the Superior craton suggested direct microbial oxidation of seawater Fe2+ (aq) by microaerophilic, Fe-oxidizing bacteria (FeOB), as a driver of GIF deposition. Although Fe-rich, microfossil-bearing stromatolites are common in 1.88 Ga GIF deposits on several cratons, combined paleontological and geochemical studies have been applied only to the Gunflint Formation. Here, we present new paleontological and geochemical observations for the ca. 1.89 Ga Gibraltar Formation GIFs from the East Arm of the Great Slave Lake, Northwest Territories, Canada. Fossil morphology, Rare Earth element (REE) concentrations, and Fe isotopic compositions support Fe oxidation by FeOB at a redoxcline poised above the fair-weather wave base. Small positive Eu anomalies and positive εNd (1.89 Ga) values suggest upwelling of deep, Fe-rich, hydrothermally influenced seawater. While high [Fe2+ (aq)] combined with low atmospheric pO2 in the late Paleoproterozoic would have provided optimal conditions in shallow oceans for FeOB to precipitate Fe oxyhydroxide, these redox conditions were likely toxic to cyanobacteria. As long as local O2 production by cyanobacteria was strongly diminished, FeOB would have had to rely on an atmospheric O2 supply by diffusion to shallow seawater to oxidize Fe2+ (aq). Using a 1-D reaction dispersion model, we calculate [O2(aq)] sufficient to deplete an upwelling Fe2+ (aq) source. Our results for GIF deposition are consistent with late Paleoproterozoic pO2 estimates of ~1%-10% PAL and constraints for metabolic [O2(aq)] requirements for modern FeOB. Widespread GIF deposition at ca. 1.88 Ga appears to mark a temporally restricted episode of optimal biogeochemical conditions in Earth's history when increased hydrothermal Fe2+ (aq) sourced from the deep oceans, in combination with low mid-Paleoproterozoic atmospheric pO2, globally satisfied FeOB metabolic Fe2+ (aq) and O2(aq) requirements in shallow-marine subtidal environments above the fair-weather wave base.

A gradual Proterozoic transition from an unstable stagnant lid to the modern plate tectonic system

When did plate tectonics begin on Earth, and what preceded it? Published thermo-mechanical mantle evolution models imply that the early history of planets with a composition and size similar to Earth and Venus should be characterized by periodic mantle overturns of 30–100 Myr duration, separated by stable lid phases of 100–300 Myr. This is best described as an unstable stagnant lid because this term captures the Jekyll and Hyde duality of such worlds, which alternate between a stagnant lid sensu stricto phase between mantle overturns, and a mobile lid phase during overturns. Mantle overturn upwelling zones would rework and resurface large tracts of pre-existing Hadean crust and basalt-dominated Archean-style oceanic lithosphere (ASOL). Basal anatexis of ASOL c. 40–50 km thick (or melting within down-drips) could generate tonalite–trondhjemite–granodiorite (TTG) melts and create proto-continental nuclei, while garnet pyroxenite restites delaminate into the mantle. With further reworking, low-K tonalitic rocks would remelt to produce granodiorite and granite, completing the transfer of radioactive elements out of the lower crust. Mantle overturns would generate large-scale lateral currents in the upper mantle that would push against Archean-aged sub-continental lithospheric mantle keels, causing continental drift and orogenesis despite the absence of plate boundary forces such as slab-pull. This is corroborated by the observed displacement of Lakshmi Planum (>1000 km) on Venus, a planet with no arcs nor ridges. Recent models suggest that the Abitibi Greenstone Belt formed as an oceanic tract behind a detached ribbon continent during the partial break-up of the Southern Superior Craton and may be a sample of Archean oceanic lithosphere. The Abitibi Greenstone Belt has c. 50 km of apparent stratigraphy composed of 2–10 Myr mafic–felsic bimodal volcanic cycles that follow assimilation–fractionation trends indicating the contamination of mantle-derived basalts with TTG-like anatectites derived from older basalts. ASOL of this type would be difficult to subduct due to its weakness and buoyancy, but would be fertile and could generate large amounts of second-stage melts. There are no sheeted dykes, precluding a seafloor spreading model, while the absence of basal cumulates or attached mantle means that this type of ASOL should not be called an ophiolite. Archean–Proterozoic unconformities are followed by the deposition of iron formations, clastic and volcanic rocks, which are only rarely affected by sagduction. The increase in siliciclastic input and decreasing sagduction reflect near-global Late Archean emergence of stiffening granitic continents from the oceans due to secular cooling and intra-continental differentiation. Albeit associated with continent-derived siliciclastic debris, many Paleoproterozoic volcanic (and plutonic) rocks resemble Archean rocks geochemically. The similarity of magmatic rocks and hot orogenic styles in the Archean and Paleoproterozoic could imply that the overall geodynamic regime was similar in both. The Siderian–Rhyacian quiet period could therefore represent a stagnant lid phase that followed the 2.5 Ga Archean overturn. When the next mantle overturn ruptured the lid at c. 2.2–2.0 Ga (and again at c. 1.9–1.8 Ga), continents would have been set into motion, forming arcs and ridges. Once initiated, arc and ridge segments needed to multiply and propagate to create a world-girdling system. Mesoproterozoic rocks preserve clear evidence of plate mobility, subduction and orogenesis, but, ophiolites, the geological record of seafloor spreading, are extremely rare prior to 1 Ga. The Earth at 2.0 Ga was probably still largely covered by ASOL, possibly similar to the Abitibi Greenstone Belt, but how and where it was all destroyed and replaced by modern oceanic lithosphere are mysteries. Given the volume of ASOL involved, recognizable by-products of this global-scale reworking process should exist. Voluminous anorthosite–mangerite–charnockite–granite/gabbro suite rocks are mostly of Proterozoic age, requiring either an ephemeral source or a unique process. Trace element inversion models applied to massif anorthosites imply they crystallized from high-La/Yb melts that do not resemble tholeiitic basalts, invalidating the notion that they are flotation cumulates from basaltic underplates. Model anorthosite-forming melts can, however, be explained by high-pressure melting of an ASOL-like basalt source with garnet-bearing residues. I posit that massif anorthosites record the destruction of an ephemeral source (ASOL) at Proterozoic convergent margins. When the last ASOL was crushed between converging continents or consumed by an overprinting arc ( c. 0.8–1 Ga), anorthosite–mangerite–charnockite–granite/gabbro suite rocks ceased to form and the Earth became a modern plate tectonic planet.

Cyanobacteria-ferrihydrite aggregates, BIF sedimentation and implications for Archaean- Palaeoproterozoic seawater geochemistry

Abstract Precambrian banded iron formations (BIFs) are iron- and silica-rich (bio)chemical sediments that are widely believed to have been precipitated by microbial oxidation of dissolved Fe(II). The by-product of these metabolisms – insoluble ferric iron – would have settled through the water column, often as aggregates with the cell biomass. While the mineralogy, composition and physical properties of cell-iron mineral aggregates formed by anaerobic Fe(II)-oxidising photoferrotrophic bacteria have been extensively studied, there are limited studies that characterise cyanobacteria-iron mineral aggregates that formed during oxygenic photosynthesis. This gap in knowledge is important because it impacts sedimentation velocities and the Fe(III) to organic carbon (Corg) ratios in the marine sediment pile. Here, we used a recently introduced approach to precisely measure the sedimentation velocity of cyanobacteria-ferrihydrite aggregates and the Fe(III):Corg ratios of the cyanobacteria-ferrihydrite aggregates over a wide range of pH and initial Fe(II) concentrations under predicted Palaeoproterozoic atmospheric conditions. Our results indicate that it was highly unlikely BIFs formed at pH <7 via chemical oxidation due to the insufficient sedimentation velocity, even at the maximum predicted Fe(II) concentration of 1800 μM with excess oxygen. Instead, large Banded Iron Formation (BIF) deposits, such as those associated with the ca. 2.47 Ga Kuruman Formation in South Africa, would only had been deposited at minimum Fe(II) concentrations of 500 μM at pH 7 or 250 μM at pH 8. The Fe:Corg ratios in cyanobacteria-ferrihydrite sediments formed during initially anoxic Fe(II) oxidation experiments represent the maximum values under each condition because we specifically extracted samples after all Fe(II) was oxidised. The Fe(III) to organic carbon ratio was consistently below 4, which is also the ratio required for dissimilatory Fe(III) reduction (DIR). This result indicates that biomass in this case was in excess, which contradicts the low organic carbon content seen in most BIFs. Thus, we suggest that biomass was either physically separated from ferrihydrite aggregates during sedimentation under the influence of ocean currents and waves, or it was degraded prior to DIR. The mineralogical and geochemical evidences of both oxide and carbonate facies from the Kuruman Iron Formation (IF) suggest that ferrihydrite was most likely the precursor along with a significant initial organic carbon input, supporting the proposed cyanobacterially-mediated BIF depositional model and experimental results.

Sediment-redox dynamics in an oligotrophic deep-water lake in Tierra del Fuego: insights from Fe isotopes

For long time in the history of Earth, ferruginous conditions governed the oceans. With the rise of oxygen during the Proterozoic era and the subsequent evolution of living organisms, worldwide deposition of iron formations occurred. These sedimentary units reveal the transition into oxic oceans, passing by local and transitory euxinic conditions, especially in coastal shelves. Constraining the iron cycle and the biogeochemical processes occurring in present and past ferruginous basins helps answering some of the question regarding global oxygenation, the evolution of life and past climate changes. Therefore, Fe speciation and Fe isotopes in both Proterozoic and recent sedimentary records have been widely used to reconstruct past basin dynamics and redox conditions in the sediment–water interface. However, sedimentation and early diagenesis can alter paleoredox proxies and their primary climate signals. In this work, we disentangled alteration processes occurring at the redox front below the sediment–water interface of a ventilated deep-water lake (Lago Fagnano, Argentina/Chile). A sequential extraction protocol was applied to characterize two reactive Fe pools: Fe oxyhydroxides and reduced iron. Subsequently, Fe isotopes were constrained to determine the main processes mobilizing Fe. At the redox front, ferric minerals reach a δ56Fe value of − 1.3‰ resulting from oxidation of dissolved Fe likely following a Rayleigh distillation effect. Dissolved Fe is produced right below via Fe reduction, as shown by the low ferric Fe content. Our observations delineate a redox cycle and a redox horizon undergoing constant upward migration, initiated by regular sedimentation. However, during events of increased rapid sedimentation (e.g., seismites) this dynamic cycle is interrupted inducing full or partial preservation of the Fe-rich redox front. In such case, oxidation of dissolved Fe is interrupted and can be recycled in ferrous minerals, such as Fe monosulfides and amorphous phases with δ56Fe values down to − 1.7 ‰. These findings have significant implications for the recording of biogeochemical cycles in the geological past, the use of Fe isotopes in freshwater-lake sediments for paleoclimate studies, and the progress of our knowledge regarding the geochemistry of past oceans.

Surface water oxygenation and low bioproductivity during deposition of iron formation of the Jacadigo Group (Brazil): Insights from combined cadmium – Chromium isotopes

The Banda Alta Formation (Urucum district, Mato Grosso do Sul, Brazil) comprises ∼600 Ma Fe and Mn deposits, which are among the world's youngest and largest Neoproterozoic sedimentary Fe and Mn formations (IF; MnF). These have been deposited in a redox-stratified, marine sub-basin (Jacadigo Basin), which was strongly influenced by glacial advance/retraction cycles with temporary influx of continental freshwater and upwelling of metal-enriched deep anoxic seawater. Cr and Cd isotopes measured on meticulously separated hematite mesobands from drill core samples are relatively homogenous throughout the ca. 325 m thick sequence sampled in the Banda Alta Fm., with average authigenic δ53Cr values of +0.93 ± 0.24 ‰ (2σ; n = 23) and δ114Cd values of −0.14 ± 0.14 ‰ (2σ; n = 15). The significant enrichment of Cr, in parallel with the strong enrichments of other redox sensitive elements (U, Mo), attests for effective and efficient reduction removal processes in the surface waters during cycles where upwelling Fe2+-rich waters reached the oxygenated surface layer exposed to the atmosphere during episodic glacier retreat stages. Assuming a similar quantitative and efficient removal pathway of dissolved Cd by iron oxyhydroxides, the so-inferred average δ114Cd signature of −0.14 ± 0.14 ‰ in the Jacadigo Basin surface water is significantly lower than signatures of modern ocean surface waters with a range of δ114Cd of ca. ∼0.4 to ∼1 ‰ and even lower than the signature of modern ocean deep waters with δ114Cd of ∼0.3 ‰. It possibly attests to reduced primary production levels and lower nutrient utilization rates during deposition of the Late Neoproterozoic Jacadigo Group, compared to today. This despite the inferred oxidized surface water layer that must have prevailed during this time, as implied by the strongly positively fractionated Cr isotope signatures and pronouncedly negative Ce-anomalies recorded in the seawater-like, shale-normalized Rare Earth Element and Yttrium (REY) patterns exhibited by the hematite mesobands. Data presented herein speak for: (1) a stable, isotopically heavy Cr input to the Jacadigo Basin at the time of deposition, implying high atmospheric O2 levels in the Late Neoproterozoic (2) likely quantitative, reductive incorporation / adsorption processes of dissolved Cr and Cd, respectively, into/onto precipitating iron oxyhydroxides, and (3) the prevalence of low nutrient concentrations and utilization rates in the Jacadigo Basin during glacier retreat cycles. Banded iron formations are considered suitable archives for reconstructing redox and bioproductivity levels in past marine depositional basin, including those prevalent in Neoproterozoic glacial conditions, via employing the CrCd isotope double tracer to iron-rich mesobands.

The role of polyphase deformation in the formation of iron deposits and gold mineralization in the paleoproterozoic nyong complex greenstone belt (Southwestern Cameroon)

The Toko-Nlonkeng area is situated in the Nyong Complex of the northwestern Congo craton. In this study, airborne geophysical data (radiometric and magnetic) and structural data (outcrops and core samples) were used to investigate the relationship between structural evolution, iron formation (IFs)-hosted iron ore deposits, and gold mineralization in the Paleoproterozoic Nyong complex greenstone belt in southwestern Cameroon. Magnetic and radiometric trends, combined with field data, show general NE-SW, NW-SE, and E-W directions that correlate with the main gold-bearing structures. The study area has undergone four (04) deformation phases relating to polycyclic metamorphic and magmatic events. The D1 and D2 phases are the result of progressive ductile and transpressional deformation; D3 is a brittle-ductile deformation; and D4 is essentially brittle with various types of fracture networks late to post-orogenic. The D3 deformation phase is characterized by constrictive deformation with C3 shears and meso‑ to mega-P3-folds, and the main stress axes show φσ2 > φσ1> φσ3, reflecting a shearing tectonic regime with a maximum E-W shortening. This polyphase deformation is derived from the Eburnean/Trans-Amazonian deformation related to the collision between the Congo and São Francisco cratons. The main strain in the structural style of the Nyong Complex appears to be transpressive tectonics. This study reveals that iron ore and gold mineralization were mostly found on the hinges of folds and confirms that folding shear zones controlled the iron ore and gold target in the Nyong Complex and Northeast Brazil. The study proposes an approach to optimize future exploration activity based on the integration of the data.

Geochemistry and depositional environment of the Neoproterozoic Ereen and Dartsagt banded iron formation (BIF) deposits in the Idermeg terrane, eastern Mongolia

Geochemistry and depositional environment of the Neoproterozoic Ereen and Dartsagt banded iron formation (BIF) deposits in the Idermeg terrane, eastern Mongolia

Mineralization products of iron-reducing bacteria and their implications to Iron Formations deposition

Mineralization products of iron-reducing bacteria and their implications to Iron Formations deposition

Marble trace element and C-O isotope geochemistry of the Paleoproterozoic Jingshan Group, North China: Insights into BIF formation during the Lomagundi-Jatuli Event

The North China Craton, one of the oldest continental blocks in the world, comprises Paleoproterozoic metamorphic sedimentary formations that record the effects of multiple major events in early Earth history, including the Great Oxidation Event (GOE) and its consequent Lomagundi-Jatuli carbon isotope event (LJE). The lack of focused research on the geological record of LJE-equivalent rocks of the Jiaodong Peninsula, Shandong Province, eastern China, has hindered our understanding of the Precambrian atmospheric oxygen evolution recorded by rocks of the North China Craton. This paper considers carbon and oxygen isotope and trace element geochemical data recovered from marble deposits of the Paleoproterozoic Jingshan Group (2.20–1.90 Ga) of the Jiaolai Basin. The investigated strata display a pronounced positive δ13CV-PDB excursion greater than 4.2 ‰. δ13CV-PDB and δ18OV-SMOW values range from −3.7 ‰ to 5.4 ‰ and 4.5 ‰ to 18.7 ‰, respectively. Positive co-variance of carbon and oxygen isotope values of the analyzed Jingshan Group samples is interpreted to reflect the effects of metamorphism and water–rock reactions. Marble deposits of the Jingshan Group experienced recrystallization, metamorphism, and silicification resulting in strong decarbonation. High amphibolite facies metamorphism may have reduced δ13CV-PDB by 3 ‰ to 5 ‰. Thus, estimated original sedimentary δ13CV-PDB values of as great as +8.4 ‰ suggest the existence of a strong positive anomaly that may reflect the global Lomagundi-Jatuli event. Rare earth and other trace element geochemical results of the present study suggest that banded iron formation (BIF) deposits associated with the Jingshan Group marble formed in a redox stratified ocean in the Jiaolai Basin dominated by ferruginous conditions. Moreover, our results suggest that positive carbon isotope anomaly associated with the LJE is largely constrained to sediment deposited in shallow and coastal marine environments.

Iron precipitation under controlled oxygen flow: Mineralogical implications for BIF precursors in the Archean ocean

Banded iron formation (BIF) deposition in the Archean ocean is thought to have been initiated by the oxidation of dissolved iron into ferric primary precursor phases that descended through the water column and were deposited on the seafloor. Effective interpretation of the trace element and isotopic composition of BIFs in the geologic record requires an understanding of the identity and longevity of those precursor phases. Temporal and spatial variation in oxidant concentration and ocean chemistry may have driven precursor mineralogy. Furthermore, precursor phases may undergo transitions during descent and burial. This experimental study follows the evolution of iron mineralogy, speciation, and redox state during the precipitation of iron under variable oxygen fluxes and in fluids containing different iron-complexing anions (chloride, sulfate, and phosphate). Additionally, suspensions collected after incomplete oxidation were anoxically aged to simulate changes to precursor mineralogy during descent below the seawater redoxcline.Results from X-ray diffraction, sequential dissolution, colorimetric determination of Fe redox state, and Fe K-edge X-ray absorption fine structure spectroscopy showed that under all experimental conditions, intermediate precipitates collected before complete iron uptake contained mineralized ferrous iron. Purely ferric mineral assemblages were not observed until iron was removed from solution. In low-oxygen experiments, intermediate precipitates contained phases with stoichiometric Fe2+, including magnetite, vivianite, and green rust (GR). Chloride green rust (GR1) had more ferric iron than sulfate green rust (GR2) and more readily transitioned to magnetite via disproportionation. GR2 was stable over a broader range of iron uptake; magnetite appeared mainly as an additional oxidation product in sulfate solution. In high oxygen experiments, mineralized ferrous iron occurred in amorphous phases or as a non-stoichiometric component in ferric oxides; final ferric assemblages were less crystalline than in low-oxygen equivalents.Low concentrations of phosphate increased the total iron oxidation rate, but also increased the ferrous content of intermediate precipitates. The incorporation of phosphate stabilized GR2 and facilitated GR2 precipitation over a larger range of iron uptake. In higher concentrations of phosphate, vivianite and poorly crystalline ferric hydroxides formed in place of GR. These findings suggest that over a range of possible ocean chemistries, mixed-valence phases may have been short lived but relevant precursors to BIF. Additionally, anionic chemistry and oxidant concentration are shown to influence the crystallinity and chemical resistivity of final ferric assemblages, affecting their reactivity during later anoxic burial.

Cyclic tidalites and seismites at a submarine hydrothermal system for a 2450 Ma banded iron formation, Hamersley Basin, Western Australia

The Hamersley Group in the Hamersley Basin, Western Australia, contains major deposits of banded iron formation of Neoarchean–Paleoproterozoic age (2629–2449 Ma). The 2450 Ma Weeli Wolli Formation near the top of the group includes banded iron formation with microbands (≤0.05–0.5 mm to rarely 1 mm thick) of chert and iron oxide lamina couplets that display distinctive cycles. Some adjacent, thin microbands have merged with compaction and the diagenetic removal of chert laminae, and maximum counts of cycle period by different studies is preferred, suggesting a period of ∼28 ± 2 microbands. Associated cyclic iron formation shows soft-sediment plastic deformation and brittle fracturing. Rare earth element geochemistry indicates that much of the iron in late Archean–early Paleoproterozoic banded iron formations was derived from submarine hydrothermal systems. Monitoring of hydrothermal vents on mid-ocean ridges and seamounts has identified tidal modulation of the discharge, temperature and dispersal of deep-sea hydrothermal plumes principally by semidiurnal variations in tidal loading and earth tides. Microearthquake swarms are associated with deep-sea hydrothermal systems at the crests of mid-ocean ridges, and tidal triggering of microearthquake activity is indicated for a hydrothermal system on the East Pacific Rise. The microband cycles in the Weeli Wolli Formation are interpreted as tidalites, comprising ∼28 ± 2 semidiurnal microbands per lunar (synodic) fortnightly cycle, related to the tidally modulated activity of a submarine hydrothermal system. The associated plastically deformed and brittle-fractured sediments are viewed as seismites resulting from microearthquakes also related to the hydrothermal system. The Weeli Wolli microband cycles and seismites may represent a rarely identified instance of iron-formation deposition near a submarine hydrothermal system. KEY POINTS Submarine hydrothermal venting was a major source of iron in late Archean–early Paleoproterozoic banded iron formations. Semidiurnal variations in tidal loading and earth tides commonly modulate present-day deep-sea hydrothermal activity, and microearthquake swarms are associated with deep-sea hydrothermal systems. Early Paleoproterozoic banded iron formation from the Hamersley Basin displays cycles with an estimated period of ∼28 ± 2 microbands and associated plastic deformation and brittle fracturing. The microband cycles are interpreted as tidalites comprising ∼28 ± 2 semidiurnal increments grouped in fortnightly cycles at a tidally modulated submarine hydrothermal system, and the deformed sediments as seismites caused by related microearthquake activity.

Archean to early Paleoproterozoic iron formations document a transition in iron oxidation mechanisms

It is generally accepted that photosynthetic marine planktonic bacteria were responsible for the oxidation of dissolved ferrous iron (Fe(II)) and the subsequent deposition of iron formations (IFs) throughout the Archean and early Paleoproterozoic. However, the relative roles of the different biological Fe oxidation mechanisms in driving IF deposition—such as anoxygenic photosynthesis (photoferrotrophs) and oxygenic photosynthesis (cyanobacteria)—remain poorly resolved. Here, we present coupled bulk-rock Fe isotope and manganese (Mn) versus Fe ratios from Archean to early Paleoproterozoic IFs in order to provide a new perspective on Earth’s early redox history and processes leading to IF deposition. Based on this updated IF geochemical record, we bolster the case that the partial oxidation of Fe(II) to Fe(III) was central to IF genesis, arguing against extensive water column Fe(II) silicate formation as the main process driving IF deposition. The geochemistry of IFs deposited prior to the Great Oxidation Event (GOE) shows that partial Fe(II) oxidation was a common feature in either anoxic or low oxygen (O2) conditions, where metabolic Fe(II) oxidation by photoferrotrophs is likely to have prevailed over ambient Fe(II) oxidation by O2 produced by cyanobacteria. Assuming that cyanobacteria evolved in the Archean, the presence of partial Fe(II) oxidation suggests that O2 production was relatively muted during this time. This points to a model for Archean surface redox conditions, whereby oxygen oases were relatively limited in extent, likely due to low primary productivity of cyanobacteria and high Fe fluxes. We further demonstrate a gradual displacement of metabolic Fe(II) oxidation in the Archean by quantitative O2-driven Fe(II) oxidation during the GOE by ca. 2.31 Ga.

Origin of the Cryogenian iron formations: Climatic fluctuation coupling with local hydrothermal iron input

The brief resurgence of iron formation deposition during the Neoproterozoic Era appears to have been closely associated with the glaciation deposits. However, the genesis of these Cryogenian iron formations (CIFs) remains unclear. Here, we present Fe isotopic compositions and rare earth element (REE) contents for four Fulu iron formation (IF) lithostratigraphic sequences in the Sanjiang area, South China. The Fulu IF strata are in conformable contact with the underlying Chang’an glacial succession. However, owing to lack of glacial deposits evidence, they are interpreted to have formed in non-glacial conditions, probably during a warm period Sturtian glaciation. Because of the shrinking ice cover over the ocean surface, more oxidants have been transferred from the atmosphere to the ocean during this Sturtian warm period, leading to reconstruction of a redox-stratified ocean. Local hydrothermal vent systems provided dissolved Fe(II) to form the IFs, as inferred from the δ56Fe values and Eu anomalies of the Fulu IFs. Our results allow us to propose a new genetic model for the origin of CIFs; whereby partial Fe(II) oxidation caused the precipitation of Fe(III) oxide and enabled the deposition of CIFs. This occurred under redox-stratified conditions over an extended warm climatic period in combination with iron sourced from local hydrothermal activities during Cryogenian glaciations.

Iron isotope fractionation in anoxygenic phototrophic Fe(II) oxidation by Rhodobacter ferrooxidans SW2

Microbially mediated Fe(II) oxidation is one of the most important pathways of Fe redox cycling on both present and early Earth. It was proposed to participate in iron formations (IFs) deposition under oxygen-depleted oceanic conditions before the Great Oxidation Event (GOE). Fe isotopic records in IFs provide important archives for the redox state of iron pool in paleo oceans. There have been a number of iron-oxidizing experiments which used bacteria with different metabolic pathways. However, it still needs further research on how and to what extent Fe isotopes are fractionated during Fe(II) oxidation mediated by the anoxygenic phototrophic Fe(II)-oxidizer, as well as its implications for the redox state of iron pool in paleo oceans. Here, we report Fe isotope fractionation between Fe(II)aq and Fe(III) (oxyhydr)oxides precipitates produced by the anoxygenic phototrophic Fe(II)-oxidizer Rhodobacter ferrooxidans SW2 at ambient temperature (20 °C). Mössbauer spectroscopy analyses indicated that the final mineral product was ferrihydrite. The corrected Fe isotope fractionation between Fe(II)aq and precipitates (Δ56Feprecipitate–Fe(II)aq) ranged from ca. −0.37 ± 0.04‰ (2se, N = 2) after 1 day of cultivation to 2.96 ± 0.17‰ (2se, N = 2) after 22 days of cultivation. The observed fractionation cannot be explained by neither a simple Rayleigh nor equilibrium process, but likely recorded a process from an isotopic disequilibrium reaching complete or near-complete equilibrium during 22 days of cultivation. The lower precipitation rate after 7 days, small size of oxidation products and dissolution-oxidation-reprecipitation processes probably promoted isotope exchange overwhelming the kinetic effect, resulting in a final isotope equilibrium between precipitates and Fe(II)aq. It revealed that the ferrihydrite produced by Fe(II) oxidation by anoxygenic photoferrotrophy could reach Fe isotope equilibrium relatively easily, thus IFs may record Fe isotope equilibrium with the fluids from which they precipitated, i.e. in some cases solely from seawater in Archean oceans.

2470 million-year-old banded iron formation reveals a climatic oscillation consistent with the Gleissberg solar cycle

Modern-day solar cycles due to the solar magnetic field oscillation are well recognized. Owing to the response of Earth’s climate to solar activity fluctuation, solar cycles in the Phanerozoic Eon have been recorded by laminites and fossil tree rings. However, the existence of magnetic cycles within the Sun younger than 3100 million-year-old is still unknown. The deposition of Precambrian banded iron formations (BIFs) reflects the primary productivity of the early ferruginous oceans and is coupled to climatic fluctuations. Here we apply synchrotron-radiation-based µ-XRF with a 20 µm interval on a 60 mm long, 2470 million-year-old BIF from the Kuruman Formation, South Africa. Our spectral analyses of multiple elemental concentration series reveal prominent and consistent 80-year cyclicity, which is best explained by the Gleissberg solar cycle. We hypothesize that solar cycles have already modulated the early Paleoproterozoic climate mainly through high energy irradiance coupled solar radiative forcing oscillation and the solar magnetic field controlled galactic cosmic ray fluctuation. Our result provides the record of solar magnetic field oscillations with stable and close-to-present cycle durations at least since the beginning of the Paleoproterozoic Era.

Diamictitic iron formation (DIF) deposits of the Neoproterozoic Nova Aurora Iron District (Macaúbas Group, Southeast Brazil)

The best-known Neoproterozoic glaciation-related iron deposits are the Rapitan-type banded iron formation (BIF) formed dominantly by chemical-sedimentary processes. We present a detailed study on a distinct type of glaciation-related iron deposit: the iron-rich metadiamictites of the Nova Aurora Iron District, comprising over 20 billion tons of iron oxide-rich rocks: the diamictitic iron formations (DIF >15 wt% Fe) and ferruginous metadiamictites (FD: 5–15 wt% Fe). Drill core logging, field mapping and analytical data revealed the protoliths, sediment sources, depositional environment, and ore enrichment processes on the iron district, and were used to discuss differences between the studied DIF and classic Rapitan-type BIF. U–Pb age spectra and Lu–Hf data for detrital zircon grains revealed a wide range of sediment sources and a maximum depositional age around 879 Ma. These data support correlations of the Nova Aurora iron deposits with the Cryogenian Macaúbas rift, a basin filled by glaciomarine successions related to the Sturtian glaciation event. The matrices of prevailing hematite-rich metadiamictites comprise (in vol %): hematite (7–55), quartz (17–57), muscovite (2–40), carbonate (<1–30), biotite (<1–18), chlorite (<1–23), epidote (<1–7), magnetite (1–5), and traces of tourmaline (<3), apatite (<3) and zircon (<1), with hematite, mica and stretched quartz outlining the metamorphic foliation. Clasts are free of iron-rich rocks. Hematite reconcentration (>50 wt% Fe) occurs in local mylonitic shear zones and tightly crenulated bands after gangue minerals removal during deformation. Late hydrothermal alteration formed magnetite-rich metadiamictite in high-strain zones. From base to top, the stratigraphic type-section of the Nova Aurora Iron District shows barren metadiamictite with quartz-rich matrix and graded-bedded quartzite lenses, followed by hematite-rich-matrix metadiamictite, then passing to muscovite-rich-matrix metadiamictite gradually richer in magnetite and sulfide, enclosing metapelite lenses. This section presents a fining-up graded-bedded succession with clasts size decreasing upwards and recurrent load structures, typical of debris flows and turbiditic sedimentation. The hematite/mica, Fe/Al, Fe/Ti and Fe/REE ratios, as well as the biotite/muscovite and silicate/sulfide ratios, which accompany variations in the oxidizing conditions, decrease to the top. Accordingly, the early protoliths were quartz-rich diamictites that passed to iron-rich diamictites and then to clay-rich, and under more reducing conditions, sulfide-bearing diamictites. Sedimentological and geochemical evidences suggest ferrous-iron accumulation followed by iron oxide precipitation from seawater when the conditions changed from anoxic to oxidizing by the input of oxygen-rich waters from deglaciation, followed by increasing reducing conditions accompanying marine transgression. These processes took place in a relatively restricted sector of the glaciomarine basin, probably a graben of the Cryogenian Macaúbas rift. Differences in relation to the classic Rapitan-type iron formations are the coarse-grained (ruditic) texture and the massive structure, the high-energy sedimentary environment, and the absence of true BIF in the Nova Aurora DIF deposits.

Cryogenian glaciostatic and eustatic fluctuations and massive Marinoan-related deposition of Fe and Mn in the Urucum District, Brazil

Abstract Global Neoproterozoic glaciations are related to extreme environmental changes and the reprise of iron formation in the rock record. However, the lack of narrow age constraints on Cryogenian successions bearing iron-formation deposits prevents correlation and understanding of these deposits on a global scale. Our new multiproxy data reveal a long Cryogenian record for the Jacadigo Group (Urucum District, Brazil) spanning the Sturtian and Marinoan ice ages. Deposition of the basal sequence of the Urucum Formation was influenced by Sturtian continental glaciation and was followed by a transgressive interglacial record of &amp;gt;600 m of carbonates that terminates in a glacioeustatic unconformity. Overlying this, there are up to 500 m of shale and sandstone interpreted as coeval to global Marinoan glacial advance. Glacial outwash delta deposits at the top of the formation correlate with diamictite-filled paleovalleys and are covered by massive Fe and Mn deposits of the Santa Cruz Formation and local carbonate. This second transgression is related to Marinoan deglaciation. Detrital zircon provenance supports glaciostatic control on Cryogenian sedimentary yield at the margins of the Amazon craton. These findings reveal the sedimentary response to two marked events of glacioeustatic incision and transgression, culminating in massive banded iron deposition during the Marinoan cryochron.

Insights into characterization and genesis of the Tieshanmiao banded iron formation deposit, China: Evidence from zircon U–Pb dating and geochemistry

The Tieshanmiao hosted by the metamorphosed Paleoproterozoic Upper Taihua Group, is a large-scale BIF–hosted Fe deposit in the southern margin of the North China Craton. The formation age, BIF type, depositional condition as well as the genesis of pyroxene–rich BIF is under heated debate. In this study, we present petrology, whole–rock geochemistry, zircon U–Pb geochronology and Lu–Hf isotope analyses on the Tieshanmiao Fe deposit. The Fe ore of the deposit can be divided into two sub-types, including banded pyroxene–magnetite quartzite (BMQ) and disseminated magnetite pyroxenite (DMP). The hanging wall rock pyroxene biotite gneiss yields an upper intercept age of 2406 ± 24 Ma, interpreted as the lower limited age for BIF deposition. The foot wall rock garnet–bearing biotite plagioclase gneiss yields a weighted mean 207Pb/206Pb age of 2739 ± 12 Ma, interpreted as its maximal depositional age. Lu-Hf isotope systematics indicates that pyroxene biotite gneiss is derived from the Paleoproterozoic mantle contaminated by the crust, and the provenance of garnet–bearing biotite plagioclase gneiss is derived from a Mesoarchean crust.The primary mineral assemblages of the pyroxene–rich Tieshanmiao Fe deposit are Fe–silicate, Ca/Mg–carbonate, ferrihydrite, and minor quartz. The BMQs have high and variable Y/Ho ratios (40–80), recording periodic alkaline hydrothermal injection that is progressively diluted by seawater, while the DMPs have low and constrained Y/Ho ratios, archiving well–supplied alkaline hydrothermal injection. We propose a REY (lanthanide elements and Y) modelling of multi–Fe sources for the Tieshanmiao BIF deposit. The BMQs are sourced from seawater and high–T hydrothermal fluid, while the DMPs are sourced from seawater, high–T hydrothermal fluids and one or several additional Fe fluxes (e.g. high-Fe dissolved riverine fluxes, low–T hydrothermal fluids or benthic Fe shuttles driven by dissimilatory iron reduction).The basic gneisses as metabasalts associated with the Tieshanmiao Fe deposit are characterized by high–Fe assay, variable LREE enrichment, relatively depletion in Nb, Ta, Zr, Ti, Y, and Th. The geochemistry of the basic gneisses shows affinities to both MORBs and volcanic–arc basalts, indicating a back–arc basin setting of the BIF deposition. It is most likely a Superior–type BIF–hosted Fe deposit, which is formed in a back–arc basin along the craton–side continental shelf.

Hexagonal magnetite in Algoma-type banded iron formations of the ca. 2.52 Ga Baizhiyan Formation, North China: Evidence for a green rust precursor?

Abstract Banded iron formations (BIFs) are iron-rich marine chemical sedimentary rocks, and their mineralogy and geochemistry can be used to gain insights into ancient ocean chemistry and biospheric evolution. Magnetite is the major iron-bearing mineral in many BIFs (particularly in the Archean) and is variably interpreted to be of primary, early diagenetic, or metamorphic origin. Different genetic interpretations for magnetite lead to divergent pictures of the Precambrian Earth system and its evolutionary models through time. The Baizhiyan Formation of the Neoarchean Wutai Group (Shanxi, North China) features magnetite-bearing, Algoma-type BIFs deposited ca. 2.52 Ga, in the lead-up to a major period of global iron formation deposition in the Paleoproterozoic. Abundant magnetite crystals found in the silica-rich bands of these BIFs show euhedral, hexagonal morphology. We suggest that this hexagonal magnetite likely represents pseudomorphs after green rust, a mixed-valence iron hydroxy-salt formed in the water column. The rare earth element composition of the BIFs shows negligible to slightly positive Ce anomalies (CeSN/CeSN* = 1.03 ± 0.07), which is characteristic of a dominantly anoxic water column. The presence of positive Eu anomalies (EuSN/EuSN* &amp;lt;3.9) suggests a substantial influence from proximal hydrothermal fluids. The co-occurrence of siderite layers associated with the magnetite-bearing strata may indicate iron cycling associated with ferruginous bottom seawater conditions. Geochemical signatures of the Baizhiyan BIFs are consistent with the interpretation that the magnetite was transformed from metastable green rust. This green rust could have formed via several processes, including the partial oxidation of Fe(II) by molecular oxygen/photoferrotrophs, the reaction of settling ferrihydrite with Fe(II)-rich hydrothermal fluids under anoxic conditions, or local dissimilatory iron reduction. In all cases, the contribution of primary green rust to BIF formation requires iron redox cycling, and similar pseudomorphs in the form of hexagonal magnetite may be more common in the geological record. Our findings support the models in which green rust was an important primary constituent of the Precambrian iron cycle, and the potential interactions of green rust with other elements (e.g., phosphorus) should be taken into consideration when reconstructing Precambrian biogeochemical cycles.

Petrographic and isotopic studies in Kamoo area, northeast isfahan, Iran

The study area is located 5.5 km north-east of Kamo County and 30 km north-east of Meymeh, Isfahan. Kamo Index comprises an anticline with a northwest-southeast trend, the outcrop of which consists of siltstone-sandstone and Jurassic shale rocks that lie along a cretaceous unit. Based on field studies as well as petrographic and geochemical investigations, mineral assemblages and minerals in the area include chalcopyrite, pyrite, marcasite, and magnetite as primary ores and malachite, bornite, covellite, chalcocite, hematite, goethite, and hydrous iron oxides as secondary ores. The secondary ores have been formed by oxidation and biogenic processes. The primary textures are granular, disseminated, vein-shaped, and layered and the secondary textures are boxed and martitized, shear zones, replacements, and veins. Tectonic, metamorphic, and oxidation factors are involved in the formation of these textures. Due to tectonic activity in this area and the presence of faults, replacement, vein, and shear textures, which have developed after mineralization, are observed. Among alterations, hematite, propylitic, sericitic, limonitic, and kaolinitic are highly prevalent and they are important in the formation of iron deposits. The sub-alkaline granitoids of the region are related to the continental subduction-zone orogenic series. Studies on the decomposed iron samples from Kamo show that most of the samples are in the sub-alkaline series and the chemical and mineralogical composition of the magma derived from this series is calc-alkaline with a large amount of iron. According to mineralogical, lithological, and geochemical evidence and based on isotopic results, Kamo deposit is a skarn-type deposit.