Siderite cannot be used as CO2 sensor for Archaean atmospheres

It was proposed to utilize siderite FeCO3 in mid to late Archaean Superior type banded as a proxy to constrain the CO2 partial pressure of Archaean atmospheres. Implicit in this proposition is that siderite was a primary carbonate mineral that crystallized directly from Fe2+ enriched Archaean seawater, in equilibrium with atmospheric CO2. To our knowledge that proposition has not been demonstrated to be valid. We test with water-gas exchange experiments under controlled CO2 partial pressures if siderite can be stabilized as a primary mineral in Fe2+ bearing seawater. Reduced seawater proxies enriched in Fe2+ and Mn2+ are equilibrated with reduced N2-CH4-CO2-H2 gas phases with variable CO2. The solid phases stabilized in Fe2+ enriched water compositions are amorphous ferrous iron hydroxy carbonates. Crystalline siderite FeCO3 is not found to be a stable phase. The phases precipitating from Mn2+ enriched water include crystalline rhodochrosite MnCO3 and possibly amorphous Mn-enriched phases. Based on these results we advise against using siderite in banded iron formations as a CO2 sensor for the Archaean atmosphere.