Low oxygen and argon in the Neoproterozoic atmosphere at 815 Ma
Yeung, Laurence Y.
The evolution of Earth's atmosphere on >106-yr timescales is tied to that of the deep Earth. Volcanic degassing, weathering, and burial of volatile elements regulates their abundance at the surface, setting a boundary condition for the biogeochemical cycles that modulate Earth's atmosphere and climate. The atmosphere expresses this interaction through its composition; however, direct measurements of the ancient atmosphere's composition more than a million years ago are notoriously difficult to obtain. Gases trapped in ancient minerals represent a potential archive of the ancient atmosphere, but their fidelity has not been thoroughly evaluated. Both trapping and preservation artifacts may be relevant. Here, I use a multi-element approach to reanalyze recently collected fluid-inclusion data from halites purportedly containing snapshots of the ancient atmosphere as old as 815 Ma. I argue that those samples were affected by the concomitant trapping of air dissolved in brines and contaminations associated with modern air. These artifacts lead to an apparent excess in O2 and Ar. The samples may also contain signals of mass-dependent fractionation and biogeochemical cycling within the fluid inclusions. After consideration of these artifacts, this new analysis suggests that the Tonian atmosphere was likely low in O2, containing ≤10% present atmospheric levels (PAL), not ∼50% PAL as the data would suggest at face value. Low concentrations of O2 are consistent with other geochemical constraints for this time period and further imply that the majority of Neoproterozoic atmospheric oxygenation occurred after 815 Ma. In addition, the analysis reveals a surprisingly low Tonian Ar inventory—≤60% PAL—which, if accurate, challenges our understanding of the solid Earth's degassing history. When placed in context with other empirical estimates of paleo-atmospheric Ar, the data imply a period of relatively slow atmospheric Ar accumulation in the Paleo- and Meso-Proterozoic, followed by extensive degassing in the late Neoproterozoic or early Cambrian, before returning to a relatively quiescent state by the Devonian. This two-step structure resembles that for the evolution of atmospheric O2, hinting at a common driving force from the deep Earth. Some caution is warranted, however, because still more enigmatic contaminations than the ones presented here may be relevant. Gases trapped in minerals may offer important constraints on the evolution of Earth's surface, climate, and atmosphere, but potential contaminations and other confounding factors need to be considered carefully before these records can be considered quantitative.
atmospheric oxygenation; fluid inclusions; gas analysis; solid earth degassing