H₂ in Antarctic firn air: Atmospheric reconstructions and implications for anthropogenic emissions

The atmospheric history of molecular hydrogen (H₂) from 1852 to 2003 was reconstructed from measurements of firn air collected at Megadunes, Antarctica. The reconstruction shows that H₂ levels in the southern hemisphere were roughly constant near 330 parts per billion (ppb; nmol H₂ mol^-1 air) during the mid to late 1800s. Over the twentieth century, H₂ levels rose by about 70% to 550 ppb. The reconstruction shows good agreement with the H₂ atmospheric history based on firn air measurements from the South Pole. The broad trends in atmospheric H₂ over the twentieth century can be explained by increased methane oxidation and anthropogenic emissions. The H₂ rise shows no evidence of deceleration during the last quarter of the twentieth century despite an expected reduction in automotive emissions following more stringent regulations. During the late twentieth century, atmospheric CO levels decreased due to a reduction in automotive emissions. It is surprising that atmospheric H₂ did not respond similarly as automotive exhaust is thought to be the dominant source of anthropogenic H_2. The monotonic late twentieth century rise in H₂ levels is consistent with late twentieth-century flask air measurements from high southern latitudes. An additional unknown source of H₂ is needed to explain twentieth-century trends in atmospheric H₂ and to resolve the discrepancy between bottom-up and top-down estimates of the anthropogenic source term. The firn air-based atmospheric history of H₂ provides a baseline from which to assess human impact on the H₂ cycle over the last 150 y and validate models that will be used to project future trends in atmospheric composition as H₂ becomes a more common energy source.