First detection of the atomic O18 isotope in the mesosphere and lower thermosphere of Earth

In the lower atmosphere of Earth, oxygen contains a higher fraction of the heavy O18 isotope than ocean water does (Dole effect). This isotopic enrichment is a signature of biological activity, set by the equilibrium between oxygenic photosynthesis and respiratory metabolisms in terrestrial and oceanic ecosystems. While the mixing between stratospheric and tropospheric oxygen leads to a slow isotopic homogenization, little is known about the isotopic oxygen enrichment in the mesosphere and thermosphere of Earth. In situ measurements from rocket-borne air samplers are limited to altitudes below the mesopause, while higher layers have only been accessible through the analysis of the oxidation of ancient cosmic spherules. Here we report the detection of the far-infrared fine-structure lines (3P1<-3P2 and 3P0<-3P1) of O18 in absorption against the Moon, and determine the O16/O18 ratio in atomic oxygen from the mesosphere and lower thermosphere in absorption. After correcting for isotopic exchange between atomic and molecular oxygen, our values for the bulk O16/O18 ratio of 468 and 382 in February and November 2021, respectively, fall significantly below that found in solar wind samples (530±2), and encompass, within uncertainties, the corresponding ratios pertaining to the Dole effect in the troposphere (487), and those found in stratospheric ozone (429 to 466). We show that with existing technology, future, more sensitive measurements will allow us to monitor deviations from isotopic homogeneity in the mesosphere and lower thermosphere of Earth by remote sensing. We demonstrate that the collisional excitation of the fine-structure levels of the P3 ground-state triplet of O18 may compete with isotopic exchange reactions, implying a deviation from the Boltzmann distribution that would be established under local thermodynamic equilibrium