Low-phosphorus concentrations and important ferric hydroxide scavenging in Archean seawater.

The availability of nutrients in seawater, such as dissolved phosphorus (P), is thought to have regulated the evolution and activity of microbial life in Earth's early oceans. Marine concentrations of bioavailable phosphorus spanning the Archean Eon remain a topic of debate, with variable estimates indicating either low (0.04 to 0.13 µM P) or high (10 to 100 µM P) dissolved P in seawater. The large uncertainty on these estimates reflects in part a lack of clear proxy signals recorded in sedimentary rocks. Contrary to some recent views, we show here that iron formations (IFs) are reliable recorders of past phosphorus concentrations and preserved a primary seawater signature. Using measured P and iron (Fe) contents in Neoarchean IF from Carajás (Brazil), we demonstrate for the first time a clear partitioning coefficient relationship in the P-Fe systematics of this IF, which, in combination with experimental and Archean literature data, permits us to constrain Archean seawater to a mean value of 0.063 ± 0.05 µM dissolved phosphorus. Our data set suggests that low-phosphorus conditions prevailed throughout the first half of Earth's history, likely as the result of limited continental emergence and marine P removal by iron oxyhydroxide precipitation, supporting prior suggestions that changes in ancient marine P availability at the end of the Archean modulated marine productivity, and ultimately, the redox state of Earth's early oceans and atmosphere. Classification: Physical Sciences, Earth, Atmospheric and Planetary Sciences.

Anoxygenic photosynthesis linked to Neoarchean iron formations in Carajás (Brazil).

Microbial activity is often invoked as a direct or indirect contributor to the precipitation of ancient chemical sedimentary rocks such as Precambrian iron formations (IFs). Determining a specific metabolic pathway from the geological record remains a challenge, however, due to a lack of constraints on the initial conditions and microbially induced redox reactions involved in the formation of iron oxides. Thus, there is ongoing debate concerning the role of photoferrotrophy, that is the process by which inorganic carbon is fixed into organic matter using light as an energy source and Fe(II) as an electron donor, in the deposition of IFs. Here, we examine ~2.74-Ga-old Neoarchean IFs and associated carbonates from the Carajás Mineral Province, Brazil, to reconstruct redox conditions and to infer the oxidizing mechanism that allowed one of the world's largest iron deposits to form. The absence of cerium (Ce) anomalies reveals that conditions were pervasively anoxic during IF deposition, while unprecedented europium (Eu) anomalies imply that Fe was supplied by intense hydrothermal activity. A positive and homogeneous Fe isotopic signal in space and time in these IFs indicates a low degree of partial oxidation of Fe(II), which, combined with the presence of 13 C-depleted organic matter, points to a photoautotrophic metabolic driver. Collectively, our results argue in favor of reducing conditions during IF deposition and suggest anoxygenic photosynthesis as the most plausible mechanism responsible for Fe oxidation in the Carajás Basin.