Strong isotope effect in the VUV photodissociation of HOD: A possible origin of D/H isotope heterogeneity in the solar nebula

The deuterium versus hydrogen (D/H) isotopic ratios are important to understand the source of water on Earth and other terrestrial planets. However, the determinations of D/H ratios suggest a hydrogen isotopic diversity in the planetary objects of the solar system. Photochemistry has been suggested as one source of this isotope heterogeneity. Here, we have revealed the photodissociation features of the water isotopologue (HOD) at λ = 120.8 to 121.7 nm. The results show different quantum state populations of OH and OD fragments from HOD photodissociation, suggesting strong isotope effect. The branching ratios of H + OD and D + OH channels display large isotopic fractionation, with ratios of 0.70 ± 0.10 at 121.08 nm and 0.49 ± 0.10 at 121.6 nm. Because water is abundant in the solar nebula, photodissociation of HOD should be an alternative source of the D/H isotope heterogeneity. This isotope effect must be considered in the photochemical models.

Atomic oxygen in the mesosphere and lower thermosphere measured by terahertz heterodyne spectroscopy

<p>Atomic oxygen is a main component of the mesosphere and lower thermosphere (MLT). The photochemistry and the energy balance of the MLT are governed by atomic oxygen. In addition, it is a tracer for dynamical motions in the MLT. It is difficult to measure with remote sensing techniques. Concentrations can be inferred indirectly from the oxygen air glow or from observations of OH, which is involved in photochemical processes related to atomic oxygen. Such measurements have been performed with several satellite instruments such as SCIAMACHY, SABER, WINDII and OSIRIS. However, the methods are indirect and rely on photochemical models and assumptions such as quenching rates, radiative lifetimes, and reaction coefficients. The results are not always in agreement, particularly when obtained with different instruments.</p><p>We have explored an alternative approach, namely the observation of the <sup>3</sup>P<sub>1</sub> → <sup>3</sup>P<sub>2</sub> fine-structure transition of atomic oxygen at 4.7 THz (63 µm) using the German Receiver for Astronomy at Terahertz Frequencies (GREAT) on board of SOFIA, the Stratospheric Observatory for Infrared Astronomy. GREAT is a heterodyne spectrometer providing high sensitivity and high spectral resolution as low as 76 kHz. This method enables the direct measurement without involving photochemical models to derive the atomic oxygen concentration. The night-time measurements have been performed during a SOFIA flight along the west coast of the US. These are the first measurements which resolve the line shape of the 4.7-THz transition. From the spectra the concentration profiles and radiances of atomic oxygen were derived with a radiative transfer model. The observed radiances range from 1.5 to 2.2 nW cm<sup>-2 </sup>sr<sup>-1</sup> and the the altitude profiles agree within the measurement uncertainty with SABER data and the NRLMSISE-00 model [1].</p><p>In conclusion, THz heterodyne spectroscopy is a powerful method to measure atomic oxygen in the MLT. With the current progress in THz technology balloon-borne and space-borne 4.7-THz heterodyne spectrometers become feasible [2, 3]. Combining such a THz spectrometer with optical instruments similar to SABER or SCIAMACHY will be even more advantageous for the determination of atomic oxygen in the MLT.</p><p>[1] H. Richter et al., Direct measurements of atomic oxygen in the mesosphere and lower thermosphere using terahertz heterodyne spectroscopy, accepted for publication in Communications Earth & Environment (2021).</p><p>[2] M. Wienold et al, A balloon-borne 4.75 THz-heterodyne receiver to probe atomic oxygen in the atmosphere, to appear in: Proceedings of the 45<sup>th</sup> International Conference on Infrared, Millimeter, and Terahertz Waves (IRMMW-THz) (Buffalo, NY, 2020).</p><p>[3] S. P. Rea et al., The low-cost upper-atmosphere sounder (LOCUS), Proceedings of the 26th International Symposium on Space Terahertz Technology (Cambridge, MA, 2015).</p>

Direct measurements of atomic oxygen in the mesosphere and lower thermosphere using terahertz heterodyne spectroscopy

Atomic oxygen is a main component of the mesosphere and lower thermosphere of the Earth, where it governs photochemistry and energy balance and is a tracer for dynamical motions. However, its concentration is extremely difficult to measure with remote sensing techniques since atomic oxygen has few optically active transitions. Current indirect methods involve photochemical models and the results are not always in agreement, particularly when obtained with different instruments. Here we present direct measurements—independent of photochemical models—of the ground state 3P1 → 3P2 fine-structure transition of atomic oxygen at 4.7448 THz using the German Receiver for Astronomy at Terahertz Frequencies (GREAT) on board the Stratospheric Observatory for Infrared Astronomy (SOFIA). We find that our measurements of the concentration of atomic oxygen agree well with atmospheric models informed by satellite observations. We suggest that this direct observation method may be more accurate than existing indirect methods that rely on photochemical models.

Atmospheric Oxidation in the Presence of Clouds during the Deep Convective Clouds and Chemistry (DC3) Study

Deep convective clouds are critically important to the distribution of atmospheric constituents throughout the troposphere but are difficult environments to study. The Deep Convective Clouds and Chemistry (DC3) study provided the environment, platforms, and instrumentation to test oxidation chemistry around deep convective clouds and their impacts downwind. Measurements on the NASA DC-8 aircraft included those of hydroxyl (OH), hydroperoxyl (HO2), OH reactivity, and more than 100 other chemical species and atmospheric properties. OH, HO2, and OH reactivity were compared to photochemical models, some with and some without simplified heterogeneous chemistry, to test the understanding of atmospheric oxidation as encoded in the model. In general, the agreement between the observed and modeled OH, HO2, and OH reactivity were all well within the combined uncertainties for both the model without heterogeneous chemistry and the model that includes heterogeneous chemistry with small OH and HO2 uptake consistent with laboratory studies. This agreement is generally independent of the altitude, ozone photolysis rate, nitric oxide and ozone abundances, modeled OH reactivity, and aerosol and ice surface area. For a sunrise to midday flight downwind of a nighttime mesoscale convective system, the observed ozone increase is consistent with the calculated ozone production rate. Even with some observed-to-modeled discrepancies, these results provide evidence that current photochemical models, properly constrained with measurements, can generally simulate observed atmospheric oxidation processes even around clouds.