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A. V. Pathare, D. A. Paige (UCLA)
Deuterium/Hydrogen (D/H) in the Martian atmosphere is enriched relative to terrestrial Standard Mean Ocean Water (SMOW) by a factor of 5.5. Yung et al. (1) photochemically modeled the escape efficiency (R) of D relative to H and obtained 0.32. Such high R implies that Mars experienced massive water loss early in its history, and cannot have significantly exchanged with juvenile water since. But Yung et al. (1) did not consider solar cycle related variations in both exospheric temperature and ionospheric chemistry, and when we accounted for changes in solar activity we obtained R = 0.17, which as we discussed last year is consistent with episodic juvenile water resupply.
However, earlier this year Krasnopolsky et al. (2) obtained an even lower R = 0.02, based on spectroscopic measurements of deuterium which they could only reproduce by assuming that the ratio of (HD/H2) / (HDO/H2O) at the 80 km base of the exosphere was less than 10 based on Yung et al. (1). To explain this significant deviation, Krasnopolsky et al. (2) argued that partitioning of D into HD and HDO is controlled not kinetically but rather thermodynamically. However, as pointed out by Yung and Kass (3), this explanation would require an isotopic exchange rate coefficient over 10 orders of magnitude larger than that measured for this thermodynamic reaction in the laboratory.
Therefore, we explore within the confines of the more likely applicable kinetic photochemical theory whether less extreme variations in exospheric and/or lower atmospheric reaction rate constants could result in a resolution to this dilemma. For example, variations in the vertical distribution of D could allow higher densities of HD at 80 km to be consistent with the new spectroscopic observations, or changes in the tropospheric conversion of HDO into HD could lessen the predicted amount of HD at 80 km. In addition, we examine the new climatological implications of R < 0.32 upon the evolution of Martian water, as massive primordial loss followed by limited juvenile water exchange may no longer be necessary.
(1) Y. L. Yung et al., Icarus, 76, 146 (1988). (2) Krasnopolsky et al., Science, 280, 1576 (1998). (3) Yung and Kass, Science, 280, 1545 (1998).