Oxygen and carbon isotope ratios in the martian atmosphere

Oxygen and carbon isotope ratios in the martian CO₂ are key values to study evolution of volatiles on Mars. The major problems in spectroscopic determinations of these ratios on Mars are uncertainties associated with: (1) equivalent widths of the observed absorption lines, (2) line strengths in spectroscopic databases, and (3) thermal structure of the martian atmosphere during the observation. We have made special efforts to reduce all these uncertainties. We observed Mars using the Fourier Transform Spectrometer at the Canada–France–Hawaii Telescope. While the oxygen and carbon isotope ratios on Mars were byproducts in the previous observations, our observation was specifically aimed at these isotope ratios. We covered a range of 6022 to 6308 cm⁻¹ with the highest resolving power of ν/δν=3.5×10⁵ and a signal-to-noise ratio of 180 in the middle of the spectrum. The chosen spectral range involves 475 lines of the main isotope, 184 lines of ¹³CO₂, 181 lines of CO¹⁸O, and 119 lines of CO¹⁷O. (Lines with strengths exceeding 10⁻²⁷ cm at 218 K are considered here.) Due to the high spectral resolution, most of the lines are not blended. Uncertainties of retrieved isotope abundances are in inverse proportion to resolving power, signal-to-noise ratio, and square root of the number of lines. Laboratory studies of the CO₂ isotope spectra in the range of our observation achieved an accuracy of 1% in the line strengths. Detailed observations of temperature profiles using MGS/TES and data on temperature variations with local time from two GCMs are used to simulate each absorption line at various heights in each part of the instrument field of view and then sum up the results. Thermal radiation of Mars' surface and atmosphere is negligible in the chosen spectral range, and this reduces errors associated with uncertainties in the thermal structure on Mars. Using a combination of all these factors, the highest accuracy has been achieved in measuring the CO₂ isotope ratios: ¹³C/¹²C = 0.978 ± 0.020 and ¹⁸O/¹⁶O = 1.018 ± 0.018 times the terrestrial standards. Heavy isotopes in the atmosphere are enriched by nonthermal escape and sputtering, and depleted by fractionation with solid-phase reservoirs. The retrieved ratios show that isotope fractionation between CO₂ and oxygen and carbon reservoirs in the solid phase is almost balanced by nonthermal escape and sputtering of O and C from Mars.