Search Results (4)

The far-infrared absorption spectrum of monodeuterated water vapor, HD¹⁶O, is analyzed using three high-sensitivity absorption spectra recorded by high-resolution Fourier transform spectroscopy at the SOLEIL synchrotron facility. The gas sample was obtained using a 1:1 mixture of H₂O and D₂O leading to a HDO abundance close to 50%. The room temperature spectra recorded in the 50–720 cm⁻¹ range cover most of the rotational band. The sensitivity of the recordings allows for lowering by three orders of magnitude the detectivity threshold of previous absorption studies in the region. Line centers are determined with a typical accuracy of 5 × 10⁻⁵ cm⁻¹ for well-isolated lines. The combined line list of 8522 water lines is assigned to 9186 transitions of the nine stable water isotopologues (H₂^XO, HD^XO, and D₂^XO with X = 16, 17, and 18). Regarding the HD¹⁶O isotopologue, a total of 2443 transitions are presently assigned while about 530 absorption transitions were available prior to our SOLEIL recordings. The comparison with the HITRAN list of HD¹⁶O transitions is discussed in detail. The obtained set of accurate HD¹⁶O transition frequencies is merged with literature sources to generate a set of 1121 accurate empirical rotation–vibration energies for the first five vibrational states (000), (010), (100), (020), and (001). The comparison to the previous dataset from an IUPAC task group illustrates a gain in the average energy accuracy by more than one order of magnitude. Based on these levels, a recommended list of transitions between the first five vibrational states is proposed for HD¹⁶O in the 0–4650 cm⁻¹ frequency range. Full article

The rotational spectrum of the 1:1 N,N-diethylhydroxylamine-water complex has been investigated using pulsed jet Fourier transform microwave spectroscopy in the 6.5–18.5 GHz frequency region. The most stable conformer has been detected as well as the ${}^{13}$C monosubstituted isotopologues in natural abundance and the ${}^{18}$O enriched water species, allowing to determine the nitrogen nuclear quadrupole coupling constants and the molecular structure in the vibrational ground state. The molecule has a $C_s$ symmetry and the water lies in the $bc$ symmetry plane forming two hydrogen bonds with the NOH frame with length: $d_{\mathit{HOH}·\mathit{NOH}}$ = 1.974 Å and $d_{H_{2}O·\mathit{HON}}$ = 2.096 Å. From symmetry-adapted perturbation theory calculations coupled to atoms in molecule approach, the corresponding interaction energy values are estimated to be 24 and 13 kJ·mol${}^{-1}$, respectively. The great strength of the intermolecular interaction involving the nitrogen atom is in agreement with the high reactivity of hydroxylamine compounds at the nitrogen site. Full article

Stable water isotopologues in paleoclimate archives ( ${\mathsf{\delta }}^{18}\mathrm{O}$ ) have been widely used as an indicator to derive past climate variations. The modern observed spatial ${\mathsf{\delta }}^{18}\mathrm{O}$ -temperature relation in the middle and high latitudes has been used to infer the paleotemperatures changes from ice core data. However, various studies have shown that the spatial slope is larger than the temporal slope at the drill site by a factor of 2. Physically, the different spatial and temporal slope has been suggested to result from the amplified local surface air temperature cooling in the polar region at Last Glacial Maximum (LGM), according to the slope ratio equation derived in our previous study. To explicitly confirm the “polar amplification” effect in understanding the differences between temporal and spatial isotope–temperature relations, here we use the same isotope-enabled atmospheric general circulation model with a moisture-tracing module embedded to quantitatively estimate the contributions of different sources to the precipitated heavy oxygen isotopes in the middle and high latitudes. Our results show that the major sources of ${\mathsf{\delta }}^{18}\mathrm{O}$ in precipitation over middle and high latitudes are from oceans where the sea surface temperature cooling at Last Glacial Maximum (LGM) is less than −2 $°\mathrm{C}$ , while the local moisture sources with a higher cooling can be also relevant for polar regions, such as north Greenland. Additionally, the neglect of the strengthened local inversion layer strength at LGM could be the main cause for the overestimated source temperature cooling by the slope ratio equation, especially for the polar regions in the Northern Hemisphere. Full article

Stable Water Isotopologues (SWIs) are important diagnostic tracers for understanding processes in the atmosphere and the global hydrological cycle. Using eight years (2002–2009) of retrievals from Odin/SMR (Sub-Millimetre Radiometer), the global climatological features of three SWIs, H₂¹⁶O, HDO and H₂¹⁸O, the isotopic composition δD and δ¹⁸O in the stratosphere are analysed for the first time. Spatially, SWIs are found to increase with altitude due to stratospheric methane oxidation. In the tropics, highly depleted SWIs in the lower stratosphere indicate the effect of dehydration when the air comes through the cold tropopause, while, at higher latitudes, more enriched SWIs in the upper stratosphere during summer are produced and transported to the other hemisphere via the Brewer–Dobson circulation. Furthermore, we found that more H₂¹⁶O is produced over summer Northern Hemisphere and more HDO is produced over summer Southern Hemisphere. Temporally, a tape recorder in H₂¹⁶O is observed in the lower tropical stratosphere, in addition to a pronounced downward propagating seasonal signal in SWIs from the upper to the lower stratosphere over the polar regions. These observed features in SWIs are further compared to SWI-enabled model outputs. This helped to identify possible causes of model deficiencies in reproducing main stratospheric features. For instance, choosing a better advection scheme and including methane oxidation process in a specific model immediately capture the main features of stratospheric water vapor. The representation of other features, such as the observed inter-hemispheric difference of isotopic component, is also discussed. Full article