Observation of DCl and upper limit to NH3 on Venus

To search for DCl in the Venus atmosphere, a spectrum near the D³⁵Cl (1–0) R4 line at 2141.54 cm^?1 was observed using the CSHELL spectrograph at NASA IRTF. Least square fitting to the spectrum by a synthetic spectrum results in a DCl mixing ratio of 17.8 ± 6.8 ppb. Comparing to the HCl abundance of 400 ± 30 ppb (Krasnopolsky 2010a] Icarus, 208, 314–322), the DCl/HCl ratio is equal to 280 ± 110 times the terrestrial D/H = 1.56 × 10^?4. This ratio is similar to that of HDO/H₂O = 240 ± 25 times the terrestrial HDO/H₂O from the VEX/SOIR occultations at 70–110 km. Photochemistry in the Venus mesosphere converts H from HCl to that in H₂O with a rate of 1.9 × 10⁹ cm^?2 s^?1 (Krasnopolsky 2012] Icarus, 218, 230–246). The conversion involves photolysis of HCl; therefore, the photochemistry tends to enrich D/H in HCl and deplete in H₂O. Formation of the sulfuric acid clouds may affect HDO/H₂O as well. The enriched HCl moves down by mixing to the lower atmosphere where thermodynamic equilibriums for H₂ and HCl near the surface correspond to D/H = 0.71 and 0.74 times that in H₂O, respectively. Time to establish these equilibriums is estimated at ～3 years and comparable to the mixing time in the lower atmosphere. Therefore, the enriched HCl from the mesosphere gives D back to H₂O near the surface. Comparison of chemical and mixing times favors a constant HDO/H₂O up to ～100 km and DCl/HCl equal to D/H in H₂O times 0.74.Ammonia is an abundant form of nitrogen in the reducing environments. Thermodynamic equilibriums with N₂ and NO near the surface of Venus give its mixing ratio of 10^?14 and 6 × 10^?7, respectively. A spectrum of Venus near the NH₃ line at 4481.11 cm^?1 was observed at NASA IRTF and resulted in a two-sigma upper limit of 6 ppb for NH₃ above the Venus clouds. This is an improvement of the previous upper limit by a factor of 5. If ammonia exists at the ppb level or less in the lower atmosphere, it quickly dissociates in the mesosphere and weakly affects its photochemistry.