Pyrite-induced uv-photocatalytic abiotic nitrogen fixation: implications for early atmospheres and Life.

The molecular form of nitrogen, N2, is universally available but is biochemically inaccessible for life due to the strength of its triple bond. Prior to the emergence of life, there must have been an abiotic process that could fix nitrogen in a biochemically usable form. The UV photo-catalytic effects of minerals such as pyrite on nitrogen fixation have to date been overlooked. Here we show experimentally, using X-ray photoemission and infrared spectroscopies that, under a standard earth atmosphere containing nitrogen and water vapour at Earth or Martian pressures, nitrogen is fixed to pyrite as ammonium iron sulfate after merely two hours of exposure to 2,3 W/m 2 of ultraviolet irradiance in the 200-400 nm range. Our experiments show that this process exists also in the absence of UV, although about 50 times slower. The experiments also show that carbonates species are fixed on pyrite surface.

Quantifying Fenton reaction pathways driven by self-generated H2O2 on pyrite surfaces.

Oxidation of pyrite (FeS2) plays a significant role in the redox cycling of iron and sulfur on Earth and is the primary cause of acid mine drainage (AMD). It has been established that this process involves multi-step electron-transfer reactions between surface defects and adsorbed O2 and H2O, releasing sulfoxy species (e.g., S2O32-, SO42-) and ferrous iron (Fe2+) to the solution and also producing intermediate by-products, such as hydrogen peroxide (H2O2) and other reactive oxygen species (ROS), however, our understanding of the kinetics of these transient species is still limited. We investigated the kinetics of H2O2 formation in aqueous suspensions of FeS2 microparticles by monitoring, in real time, the H2O2 and dissolved O2 concentration under oxic and anoxic conditions using amperometric microsensors. Additional spectroscopic and structural analyses were done to track the dependencies between the process of FeS2 dissolution and the degradation of H2O2 through the Fenton reaction. Based on our experimental results, we built a kinetic model which explains the observed trend of H2O2, showing that FeS2 dissolution can act as a natural Fenton reagent, influencing the oxidation of third-party species during the long term evolution of geochemical systems, even in oxygen-limited environments.