Earth’s surface has undergone a protracted oxygenation, which is commonly assumed to have profoundly affected the biosphere. However, basic aspects of this history are still debated—foremost oxygen (O₂) levels in the oceans and atmosphere during the billion years leading up to the rise of algae and animals. Here we use isotope ratios of iron (Fe) in ironstones—Fe-rich sedimentary rocks deposited in nearshore marine settings—as a proxy for O₂ levels in shallow seawater. We show that partial oxidation of dissolved Fe(II) was characteristic of Proterozoic shallow marine environments, whereas younger ironstones formed via complete oxidation of Fe(II). Regardless of the Fe(II) source, partial Fe(II) oxidation requires low O₂ in the shallow oceans, settings crucial to eukaryotic evolution. Low O₂ in surface waters can be linked to markedly low atmospheric O₂—likely requiring less than 1% of modern levels. Based on our records, these conditions persisted (at least periodically) until a shift toward higher surface O₂ levels between ca. 900 and 750 Ma, coincident with an apparent rise in eukaryotic ecosystem complexity. This supports the case that a first-order shift in surface O₂ levels during this interval may have selected for life modes adapted to more oxygenated habitats. Significance Earth’s transition from anoxic oceans and atmosphere to a well-oxygenated state led to major changes in nearly every surficial system. However, estimates of surface oxygen levels in the billion years preceding this shift span two orders of magnitude, suggesting a poor understanding of the evolution of the oxygen cycle. We use the isotopic record of iron oxides deposited in ancient shallow marine environments to show that oxygen remained at extremely low levels in the ocean–atmosphere system for most of Earth’s history, and that a rise in oxygen occurred in step with the expansion of complex, eukaryotic ecosystems. These results indicate that Earth is capable of stabilizing at low atmospheric oxygen levels, with important implications for exploration of exoplanet biosignatures.

The late Neoarchean, ~2.53 to 2.51 Ga Dagushan banded iron formation (BIF), is a typical Algoma-type BIF located in the northeast part of the North China craton. Despite having undergone upper greenschist to lower amphibolite facies metamorphism, the Dagushan BIF retains evidence of varied depositional facies, making it an ideal archive to evaluate the paleomarine environment and the paragenesis of the ore minerals. A transition from oxide to silicate to carbonate facies BIF is evident in a northward direction. The mineralogical composition shifts from magnetite and quartz in the south through a magnetite-quartz-cummingtonite/stilpnomelane assemblage in the transition zone to magnetite-siderite in the north. Such a distinct distribution of mineralogical facies correlates well with the depositional environment of the BIF. The carbonate facies BIFs formed in a near-shore, proximal environment, whereas the oxide and silicate facies BIF assemblages formed in deeper waters, distal to the paleoshoreline. The BIF samples display characteristic seawater-like rare earth element + yttrium (REE + Y) profiles with positive La and Y anomalies and heavy REE enrichment relative to the light REEs when normalized to post-Archean Australian shale. Positive Eu anomalies suggest a high-temperature hydrothermal contribution to the BIF. The absence of a negative Ce anomaly in nearly all samples, coupled with positive δ⁵⁶Fe in magnetite in all mineralogical facies, indicates a dominantly anoxic water column contemporaneous with deposition of the BIF. At ~2.53 Ga in the Anshan area, seawater was mostly anoxic and rich in ferrous iron. Dissolved ferrous iron in upwelling hydrothermal fluids was oxidized and precipitated as Fe(III) oxyhydroxides in the photic zone leading to BIF formation. Proximal to hydrothermal vents, magnetite formed via the reaction of Fe(III) oxyhydroxides and aqueous Fe(II) supplied from the hydrothermal fluids and microbial dissimilatory iron reduction (DIR) coupled to organic carbon oxidation. Proximal to a paleoshoreline, siderite formed through DIR, as evidenced by the depleted δ¹³C values and the presence of graphite. Silicates, such as stilpnomelane and cummingtonite, are considered to be the metamorphic products of early diagenetic silicates (e.g., nontronite) that formed in the water column from admixtures of Fe(III) oxyhydroxides and amorphous silica.

The association of volcanogenic massive sulfide (VMS) deposits and Algoma-type banded iron formations (BIFs) in many Precambrian terranes indicates a link between submarine hydrothermal processes, seawater chemistry, and chemical sedimentation. The Neoarchean (~2.55 Ga) Qingyuan greenstone belt VMS-BIF metallogenic association, located on the north margin of the North China craton, is a typical example of such an association. The stratigraphy of the Qingyuan greenstone belt includes three units (from the oldest to youngest): (1) the Shipengzi Formation, composed of tholeiitic-transitional arc basalts with negative Nb anomalies, interlayered normal mid-ocean ridge basalts (N-MORBs) and FI-type dacites, and BIFs; (2) the Hongtoushan Formation, consisting of polycyclic bimodal suites of N-MORB-type basalts and FII-type dacites, as well as VMS mineralization and minor BIFs; and (3) the Nantianmen Formation, composed of schist, quartzite, and marble with minor basalts and BIFs. Positive Fe isotope compositions (δ⁵⁶Fe of 0.48–0.69‰) for magnetite in the silicate BIF of the Shipengzi Formation indicate partial oxidation of aqueous Fe(II). Using a dispersion-reaction model, the relatively high δ⁵⁶Fe values (0.72–1.04‰) estimated for primary ferric (oxyhydr)oxides in this BIF constrain local dissolved O₂ contents of the Neoarchean surface ocean to 10^–4 to 10^–3 μmol/L. By comparison, negative δ⁵⁶Fe values for magnetite (–0.83 to –0.65‰) in silicate BIFs of the Hongtoushan Formation and the Nantianmen Formation suggest deposition from a residual water column that was depleted in ⁵⁶Fe. Following the formation of the bulk of the VMS deposits in the Hongtoushan Formation, a significant change to positive magnetite δ⁵⁶Fe values (0.79–1.04‰) occurs in the youngest sulfide-bearing BIF in the Nantianmen Formation. This implies that the VMS-related hydrothermal vents injected a large mass of unfractionated ferrous iron into the ocean. Negative Δ³³S anomalies in sedimentary pyrite of bedded VMS ores (avg of –0.08 ± 0.007‰, n = 6) and sulfide-bearing BIFs (avg of –0.06 ± 0.007‰, n = 3) of the Qingyuan greenstone belt, along with mass-independent fractionations (with an average Δ³⁶S/Δ³³S ratio of –1.1 ± 0.3), are best explained by incorporation of seawater sulfate of atmospheric photochemical origin during their formation. The systematic differences in whole-rock geochemistry and Δ³³S values for different types of VMS ores imply variable seawater sulfate contributions to their mineralization. Our results are consistent with global anoxic conditions during the Neoarchean to Paleoproterozoic transition (i.e., at 2.5 Ga), and confirm that formation of the VMS-BIF metallogenic association took place in dominantly anoxic, ferruginous basins at different depths, with the VMS-related hydrothermal system contributing significant Fe to the deposition of BIFs.

Banded iron formations (BIFs) are among the few chemical sedimentary archives that capture the biogeochemical evolution of Fe cycling and the redox evolution of the early Earth. Although biologically recycled continental Fe has been previously proposed to be a significant source of Fe in BIFs deposited from a stratified ocean at the onset of the Great Oxidation Event (GOE; ~2.5–2.2 Ga), constraining Fe sources and pathways in Archean BIFs remains challenging. Here we present major and trace element and Fe-Nd-Cr isotope data for the largest BIF (i.e., Dataigou) in China to test whether a benthic Fe shuttle was operative during deposition of pre-GOE BIFs. The absence of true, shale-normalized Ce anomalies, coupled with unfractionated Cr and positive Fe isotope compositions, suggests that BIF deposition occurred in an anoxic water column under reducing atmospheric conditions, whereas positive Eu anomalies indicate a significant input from a high-temperature hydrothermal source. Based on a significant correlation between initial Nd and Fe isotope data, we suggest that two Fe sources were periodically mixed and resulted in deposition of the Dataigou BIF. Here, we suggest the following sources: (1) hydrothermal fluids from sea-floor systems (low $εNd(t)$ and high δ⁵⁶Fe), derived from the interaction of fluids with underlying, older continental crust, and (2) a benthic Fe flux (high $εNd(t)$ and low δ⁵⁶Fe), generated by microbial Fe(III) reduction in coastal sediments during weathering of a nearby depleted landmass. Results presented here confirm, for the first time, that a microbially driven Fe shuttle was operational and supplied Fe on a basin-wide scale in the absence of atmospheric oxygen.

Banded iron formations (BIFs) are enigmatic chemical sedimentary rocks that chronicle the geochemical and microbial cycling of iron and carbon in the Precambrian. However, the formation pathways of Fe carbonate, namely siderite, remain disputed. Here, we provide photomicrographs, Fe, C and O isotope of siderite, and organic C isotope of the whole rock from the ~2.52 Ga Dagushan BIF in the Anshan area, China, to discuss the origin of siderite. There are small magnetite grains that occur as inclusions within siderite, suggesting a diagenetic origin of the siderite. Moreover, the siderites have a wide range of iron isotope compositions (δ⁵⁶Fe_Sd) from −0.180‰ to +0.463‰, and a relatively negative C isotope composition (δ¹³C_Sd = −6.20‰ to −1.57‰). These results are compatible with the reduction of an Fe(III)-oxyhydroxide precursor to dissolved Fe(II) through microbial dissimilatory iron reduction (DIR) during early diagenesis. Partial reduction of the precursor and possible mixing with seawater Fe(II) could explain the presence of siderite with negative δ⁵⁶Fe, while sustained reaction of residual Fe(III)-oxyhydroxide could have produced siderite with positive δ⁵⁶Fe values. Bicarbonate derived from both DIR and seawater may have provided a C source for siderite formation. Our results suggest that microbial respiration played an important role in the formation of siderite in the late Archean Dagushan BIF.