Sulfur and carbon isotopic evidence for metabolic pathway evolution and a four-stepped Earth system progression across the Archean and Paleoproterozoic

Abstract The Earth's mantle has provided a ready redox gradient of sulfur compounds (SO 2 , H 2 S) since the stabilization of the crust and formation of the ocean over 4 billion years ago, and life has evolved a multitude of metabolic pathways to take advantage of this gradient. These transitions are recorded in the sulfur and carbon isotope signals preserved in the rock record, in the genomic records of extant microorganisms, and in the changing mantle and crust structure, composition and cycling. Here, we have assembled approximately 20,000 sulfur (δ 34 S, Δ 33 S, Δ 36 S) and carbon (δ 13 C) isotope data points from scientific publications spanning over five decades of geochemical analyses on rocks deposited from 4.0 to 1.5 Ga. We place these data in the context of molecular clock and tectonic and surface redox indicators to identify overarching trends and integrate them into a holistic narrative on the transition of the Earth's surface towards more oxidizing conditions. The greatest extreme in δ 34 S values of sulfide minerals (− 45.5 to 54.9‰) and sulfate minerals (− 13.6 to 46.6‰) as well as δ 13 C values in carbonate minerals (− 16.8 to 29.6‰) occurred in the period following the Great Oxidation Event (GOE), while the greatest extremes in organic carbon δ 13 C values (− 60.9 to 2.4‰) and sulfide and sulfate mineral Δ 33 S and Δ 36 S values (− 4.0 to 14.3‰ and − 12.3 to 3.2‰, respectively) occurred prior to the GOE. From our observations, we divide transitions in Earth's history into four periods: Period 1 (4.00 to 2.80 Ga) during which geochemical cycles were initialized, Period 2 (2.80 to 2.45 Ga) during which S and C isotope systems exhibit changes as conditions build up to the GOE, Period 3 (2.45 to 2.00 Ga) encompassing the GOE, and Period 4 (after 2.00 Ga) after which S and C isotopic systems remained relatively constant marking a time of Earth system geochemical quiescence. Using these periods, we link changes in S and C isotopes to molecular clock work to aid in interpreting emerging metabolic functions throughout Earth's history while underscoring the need for better proxies for robust evolutionary analyses. Specifically, results indicate: 1) an early development of sulfide oxidation and dissimilatory sulfite reduction followed by disproportionation and then sulfate reduction to sulfite resulting in a fully biologically mediated sulfur cycle by ~ 3.25 Ga; 2) support for the acetyl coenzyme-A pathway as the most likely earliest form of biologically mediated carbon fixation following methanogenesis; 3) an increasingly redox-stratified ocean in the Neoarchean with largely oxic surface water and euxinic bottom water during the first half of the Paleoproterozoic; and 4) that secular changes in Earth system crustal cycling dynamics and continent formation likely played a key role in driving the timing of the GOE. Finally, based on geochemical data, we suggest that the Paleoproterozoic be divided into a new Era of the Eoproterozoic (from 2.45 to 2.00 Ga) and the Paleoproterozoic (from 2.00 to 1.60 Ga).