Terrestrial microbialites provide constraints on the mesoproterozoic atmosphere

Palaeoclimate data indicate that Earth surface temperatures have remained largely temperate for the past 3.5 Byr despite significantly lower solar luminosity over this time relative to the present day. There is evidence for episodic early and late Proterozoic glaciation, but little evidence of glaciation in the intervening billion years. A prolonged equable Mesoproterozoic Earth requires elevated greenhouse gas concentrations. Two endmember scenarios have been proposed for maintaining global warmth. These include extremely high pCO(2) or more modest pCO(2) with higher methane concentrations. This paper reports on the delta C-13 of organic matter in 1.1 Ga stromatolites from the Copper Harbor Conglomerate (CHC) of the Mesoproterozoic Midcontinent Rift (North America) and delta O-18 and Delta(47) temperatures of inorganic stromatolite carbonate to constrain formation and burial conditions and the magnitude of ancient carbon isotope discrimination. CHC sediments have never been heated above 125-155 degrees C, providing a novel geochemical archive of the ancient environment. Stromatolite Delta(47) data record moderate alteration, and therefore, the occluded organic matter was unlikely to have experienced significant thermal alteration after deposition. The delta C-13 values of ancient mat organic matter and inorganic carbonate show isotope discrimination (epsilon(p)) values 15.5-18.5 parts per thousand, similar to modern microbial mats formed in equilibrium with low concentrations of dissolved inorganic carbon. In combination, these data are consistent with a temperate climate Mesoproterozoic biosphere supported by relatively modest pCO(2). This result agrees with Atmosphere-Ocean Global Circulation Model reconstructions for Mesoproterozoic climate using 5-10 times present atmospheric levels pCO(2) and pCH(4) of >28 ppmv. However, given marine modelling constraints of CH4 production that suggest pCH(4) was below 10 ppm, this creates a methane paradox. Either an additional source of CH4 (e.g. from terrestrial ecosystems) or another greenhouse gas, such as N2O, would have been necessary to maintain equable conditions in the Mesoproterozoic.