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A drop in the ocean Earth's bulk composition is similar to that of a group of oxygen-poor meteorites called enstatite chondrites, thought to have formed in the early solar nebula. This leads to the suggestion that proto-Earth was dry, and that volatiles including water were delivered by asteroid and comet impacts. The deuterium-to-hydrogen (D/H) ratios measured in six Oort cloud comets are much higher than on Earth, however, apparently ruling out a dominant role for such bodies. Now the Herschel Space Telescope has been used to determine the D/H ratio in the Kuiper belt comet 103P/Hartley 2. The ratio is Earth-like, suggesting that this population of comets may have contributed to Earth's ocean waters. For decades, the source of Earth's volatiles, especially water with a deuterium-to-hydrogen ratio (D/H) of (1.558 ± 0.001) × 10 −4 , has been a subject of debate. The similarity of Earth’s bulk composition to that of meteorites known as enstatite chondrites 1 suggests a dry proto-Earth 2 with subsequent delivery of volatiles 3 by local accretion 4 or impacts of asteroids or comets 5 , 6 . Previous measurements in six comets from the Oort cloud yielded a mean D/H ratio of (2.96 ± 0.25) × 10 −4 . The D/H value in carbonaceous chondrites, (1.4 ± 0.1) × 10 −4 , together with dynamical simulations, led to models in which asteroids were the main source of Earth's water 7 , with ≤10 per cent being delivered by comets. Here we report that the D/H ratio in the Jupiter-family comet 103P/Hartley 2, which originated in the Kuiper belt, is (1.61 ± 0.24) × 10 −4 . This result substantially expands the reservoir of Earth ocean-like water to include some comets, and is consistent with the emerging picture of a complex dynamical evolution of the early Solar System 8 , 9 .

With a 3.5 m diameter telescope passively cooled to approximately 80 K, and a science payload comprising two direct detection cameras/medium resolution imaging spectrometers (PACS and SPIRE) and a very high spectral resolution heterodyne spectrometer (HIFI), the Herschel Space Observatory is providing extraordinary observational opportunities in the 55-670 μm spectral range. HIFI has opened for the first time to high-resolution spectroscopy the submillimetre band that includes the fundamental rotational transitions of interstellar hydrides, the basic building blocks of astrochemistry. We discuss a recent HIFI discovery of metastable rotational transitions of the hydronium ion (protonated water, H3O+), with rotational level energies up to 1200 K above the ground state, in absorption towards Sagittarius B2(N) in the Galactic centre. Hydronium is an important molecular ion in the oxygen chemical network. Earlier HIFI observations have indicated a general deficiency of H3O+ in the diffuse gas in the Galactic disc. The presence of hot H3O+ towards Sagittarius B2(N) thus appears to be related to the unique physical conditions in the central molecular zone, manifested, for example, by the widespread presence of abundant H. One intriguing theory for the high rotational temperature characterizing the population of the H3O+ metastable levels may be formation pumping in molecular gas irradiated by X-rays emitted by the Galactic centre black hole. Alternatively, the pervasive presence of enhanced turbulence in the central molecular zone may give rise to shocks in the lower-density medium that is exposed to energetic radiation.

For decades, the source of Earth's volatiles, especially water with a deuterium-to-hydrogen ratio (D/H) of (1.558 ± 0.001) x [10.sup.-4], has been a subject of debate. The similarity of Earth's bulk composition to that of meteorites known as enstatite chondrites (1) suggests a dry proto-Earth (2) with subsequent delivery of volatiles (3) by local accretion (4) or impacts of asteroids or comets (5,6). Previous measurements in six comets from the Oort cloud yielded a mean D/H ratio of (2.96 ± 0.25) x [10.sup.-4]. The D/H value in carbonaceous chondrites, (1.4 ± 0.1) x [10.sup.-4], together with dynamical simulations, led to models in which asteroids were the main source of Earth's water (7), with ≤ 10 per cent being delivered by comets. Here we report that the D/H ratio in the Jupiter-family comet 103P/Hartley 2, which originated in the Kuiper belt, is (1.61 ± 0.24) x [10.sup.-4]. This result substantially expands the reservoir of Earth ocean-like water to include some comets, and is consistent with the emerging picture of a complex dynamical evolution of the early Solar System (8,9).

The Heterodyne Instrument for the Far Infrared (HIFI) aboard the Herschel Space Observatory has acquired high-resolution broadband molecular spectra of star-forming regions in a wavelength range that is mostly inaccessible from ground-based astronomical observatories. These spectral surveys provide new insight into the chemical composition and physical properties of molecular clouds. In this manuscript, we present initial results from the HIFI spectral survey of the Sagittarius B2(N) molecular cloud, which contains spectral features assigned to at least 40 different molecules in a range of physical environments. While extensive line blending is observed due to the chemical complexity of this region, reliable molecular line identifications can be made, down to the noise floor, due to the large number of transitions detected for each species in the 1.2 THz survey bandwidth. This allows for the extraction of new weakly emitting species from the line forest. These HIFI surveys will be an invaluable archival resource for future investigations into interstellar chemistry.

We present a comprehensive analysis of a broad band spectral line survey of the Orion Kleinmann-Low nebula (Orion KL), one of the most chemically rich regions in the Galaxy, using the HIFI instrument on board the Herschel Space Observatory. This survey spans a frequency range from 480 to 1907 GHz at a resolution of 1.1 MHz. These observations thus encompass the largest spectral coverage ever obtained toward this high-mass star-forming region in the sub-mm with high spectral resolution, and include frequencies \\(>\\) 1 THz where the Earth's atmosphere prevents observations from the ground. In all, we detect emission from 39 molecules (79 isotopologues). Combining this dataset with ground based mm spectroscopy obtained with the IRAM 30 m telescope, we model the molecular emission from the mm to the far-IR using the XCLASS program which assumes local thermodynamic equilibrium (LTE). Several molecules are also modeled with the MADEX non-LTE code. Because of the wide frequency coverage, our models are constrained by transitions over an unprecedented range in excitation energy. A reduced \\(\\chi^{2}\\) analysis indicates that models for most species reproduce the observed emission well. In particular, most complex organics are well fit by LTE implying gas densities are high (\\(>\\)10\\(^6\\) cm\\(^{-3}\\)) and excitation temperatures and column densities are well constrained. Molecular abundances are computed using H\\(_{2}\\) column densities also derived from the HIFI survey. The distribution of rotation temperatures, \\(T_{\\rm rot}\\), for molecules detected toward the hot core is significantly wider than the compact ridge, plateau, and extended ridge \\(T_{\\rm rot}\\) distributions, indicating the hot core has the most complex thermal structure.

A sensitive broadband molecular line survey of the Sagittarius B2(N) star-forming region has been obtained with the HIFI instrument on the Herschel Space Observatory, offering the first high-spectral resolution look at this well-studied source in a wavelength region largely inaccessible from the ground (625-157 um). From the roughly 8,000 spectral features in the survey, a total of 72 isotopologues arising from 44 different molecules have been identified, ranging from light hydrides to complex organics, and arising from a variety of environments from cold and diffuse to hot and dense gas. We present an LTE model to the spectral signatures of each molecule, constraining the source sizes for hot core species with complementary SMA interferometric observations, and assuming that molecules with related functional group composition are cospatial. For each molecule, a single model is given to fit all of the emission and absorption features of that species across the entire 480-1910 GHz spectral range, accounting for multiple temperature and velocity components when needed to describe the spectrum. As with other HIFI surveys toward massive star forming regions, methanol is found to contribute more integrated line intensity to the spectrum than any other species. We discuss the molecular abundances derived for the hot core, where the local thermodynamic equilibrium approximation is generally found to describe the spectrum well, in comparison to abundances derived for the same molecules in the Orion KL region from a similar HIFI survey.

Hydrogen fluoride has been established to be an excellent tracer of molecular hydrogen in diffuse clouds. In denser environments, however, the HF abundance has been shown to be approximately two orders of magnitude lower. We present Herschel/HIFI observations of HF J=1-0 toward two high-mass star formation sites, NGC6334 I and AFGL 2591. In NGC6334 I the HF line is seen in absorption in foreground clouds and the source itself, while in AFGL 2591 HF is partially in emission. We find an HF abundance with respect to H2 of 1.5e-8 in the diffuse foreground clouds, whereas in the denser parts of NGC6334 I, we derive a lower limit on the HF abundance of 5e-10. Lower HF abundances in dense clouds are most likely caused by freeze out of HF molecules onto dust grains in high-density gas. In AFGL 2591, the view of the hot core is obstructed by absorption in the massive outflow, in which HF is also very abundant 3.6e-8) due to the desorption by sputtering. These observations provide further evidence that the chemistry of interstellar fluorine is controlled by freeze out onto gas grains.

We have examined methanol emission from Orion KL with of the {\\em Herschel}/HIFI instrument, and detected two methanol bands centered at 524 GHz and 1061 GHz. The 524 GHz methanol band (observed in HIFI band 1a) is dominated by the isolated \\(\\Delta\\)J\\(=\\)0, K\\(=-4\\rightarrow\\)-3, v$_t$$=\\(0 Q branch, and includes 25 E-type and 2 A-type transitions. The 1061 GHz methanol band (observed in HIFI band 4b) is dominated by the \\)\\Delta\\(J\\)=\\(0, K\\)=7\\rightarrow\\(6, v\\)_t$$=\\(0 Q branch transitions which are mostly blended. We have used the isolated E-type v\\)_t$$=$0 methanol transitions to explore the physical conditions in the molecular gas. With HIFI's high velocity resolution, the methanol emission contributed by different spatial components along the line of sight toward Orion KL (hot core, low velocity flow, and compact ridge) can be distinguished and studied separately. The isolated transitions detected in these bands cover a broad energy range (upper state energy ranging from 80 K to 900 K), which provides a unique probe of the thermal structure in each spatial component. The observations further show that the compact ridge is externally heated. These observations demonstrate the power of methanol lines as probes of the physical conditions in warm regions in close proximity to young stars.

To investigate the accretion and feedback processes in massive star formation, we analyze the shapes of emission lines from hot molecular cores, whose asymmetries trace infall and expansion motions. The high-mass star forming region SgrB2(M) was observed with Herschel/HIFI (HEXOS key project) in various lines of HCN and its isotopologues, complemented by APEX data. The observations are compared to spherically symmetric, centrally heated models with density power-law gradient and different velocity fields (infall or infall+expansion), using the radiative transfer code RATRAN. The HCN line profiles are asymmetric, with the emission peak shifting from blue to red with increasing J and decreasing line opacity (HCN to H\\(^{13}\\)CN). This is most evident in the HCN 12--11 line at 1062 GHz. These line shapes are reproduced by a model whose velocity field changes from infall in the outer part to expansion in the inner part. The qualitative reproduction of the HCN lines suggests that infall dominates in the colder, outer regions, but expansion dominates in the warmer, inner regions. We are thus witnessing the onset of feedback in massive star formation, starting to reverse the infall and finally disrupting the whole molecular cloud. To obtain our result, the THz lines uniquely covered by HIFI were critically important.

We have observed CH absorption lines (\\(J=3/2, N=1 \\leftarrow J=1/2, N=1\\)) against the continuum source Sgr~B2(M) using the \\textit{Herschel}/HIFI instrument. With the high spectral resolution and wide velocity coverage provided by HIFI, 31 CH absorption features with different radial velocities and line widths are detected and identified. The narrower line width and lower column density clouds show `spiral arm' cloud characteristics, while the absorption component with the broadest line width and highest column density corresponds to the gas from the Sgr~B2 envelope. The observations show that each `spiral arm' harbors multiple velocity components, indicating that the clouds are not uniform and that they have internal structure. This line-of-sight through almost the entire Galaxy offers unique possibilities to study the basic chemistry of simple molecules in diffuse clouds, as a variety of different cloud classes are sampled simultaneously. We find that the linear relationship between CH and H\\(_2\\) column densities found at lower \\(A_V\\) by UV observations does not continue into the range of higher visual extinction. There, the curve flattens, which probably means that CH is depleted in the denser cores of these clouds.