Photochemistry of the PAH pyrene in water ice: the case for ion-mediated solid-state astrochemistry

Context. Icy dust grains play an important role in the formation of complex inter- and circumstellar molecules. Observational studies show that polycyclic aromatic hydrocarbons (PAHs) are abundantly present in the ISM in the gas phase. It is likely that these non-volatile species freeze out onto dust grains as well and participate in the astrochemical solid-state network, but experimental PAH ice studies are largely lacking. Methods. Near UV/VIS spectroscopy is used to track the in situ VUV driven photochemistry of pyrene containing ices at temperatures ranging from 10 to 125 K. Results. The main photoproducts of VUV photolyzed pyrene ices are spectroscopically identified and their band positions are listed for two host ices, \water and CO. Pyrene ionisation is found to be most efficient in \water ices at low temperatures. The reaction products, triplet pyrene and the 1-hydro-1-pyrenyl radical are most efficiently formed in higher temperature water ices and in low temperature CO ice. Formation routes and band strength information of the identified species are discussed. Additionally, the oscillator strengths of Py, Py^+ and PyH are derived and a quantitative kinetic analysis is performed by fitting a chemical reaction network to the experimental data. Conclusions. Pyrene is efficiently ionised in water ice at temperatures below 50 K. Hydrogenation reactions dominate the chemistry in low temperature CO ice with trace amounts of water. The results are put in an astrophysical context by determining the importance of PAH ionisation in a molecular cloud. The photoprocessing of a sample PAH in ice described in this manuscript indicates that PAH photoprocessing in the solid state should also be taken into account in astrochemical models.Comment: 11 pages, 8 figures, accepted for publication in A&

Unlocking CO Depletion in Protoplanetary Disks II. Primordial C/H Predictions Inside the CO Snowline

CO is thought to be the main reservoir of volatile carbon in protoplanetary disks, and thus the primary initial source of carbon in the atmospheres of forming giant planets. However, recent observations of protoplanetary disks point towards low volatile carbon abundances in many systems, including at radii interior to the CO snowline. One potential explanation is that gas phase carbon is chemically reprocessed into less volatile species, which are frozen on dust grain surfaces as ice. This mechanism has the potential to change the primordial C/H ratio in the gas. However, current observations primarily probe the upper layers of the disk. It is not clear if the low volatile carbon abundances extend to the midplane, where planets form. We have run a grid of 198 chemical models, exploring how the chemical reprocessing of CO depends on disk mass, dust grain size distribution, temperature, cosmic ray and X-ray ionization rate, and initial water abundance. Building on our previous work focusing on the warm molecular layer, here we analyze the results for our grid of models in the disk midplane at 12 au. We find that either an ISM level cosmic ray ionization rate or the presence of UV photons due to a low dust surface density are needed to chemically reduce the midplane CO gas abundance by at least an order of magnitude within 1 Myr. In the majority of our models CO does not undergo substantial reprocessing by in situ chemistry and there is little change in the gas phase C/H and C/O ratios over the lifetime of the typical disk. However, in the small sub-set of disks where the disk midplane is subject to a source of ionization or photolysis, the gas phase C/O ratio increases by up to nearly 9 orders of magnitude due to conversion of CO into volatile hydrocarbons.Comment: Accepted for publication in ApJ, 15 pages, 10 figures, 3 table

The ancient heritage of water ice in the solar system

Identifying the source of Earth's water is central to understanding the origins of life-fostering environments and to assessing the prevalence of such environments in space. Water throughout the solar system exhibits deuterium-to-hydrogen enrichments, a fossil relic of low-temperature, ion-derived chemistry within either (i) the parent molecular cloud or (ii) the solar nebula protoplanetary disk. Utilizing a comprehensive treatment of disk ionization, we find that ion-driven deuterium pathways are inefficient, curtailing the disk's deuterated water formation and its viability as the sole source for the solar system's water. This finding implies that if the solar system's formation was typical, abundant interstellar ices are available to all nascent planetary systems.Comment: 33 pages, 7 figures including main text and supplementary materials. Published in Scienc

Exploring the Origins of Deuterium Enrichments in Solar Nebular Organics

Deuterium-to-hydrogen (D/H) enrichments in molecular species provide clues about their original formation environment. The organic materials in primitive solar system bodies have generally higher D/H ratios and show greater D/H variation when compared to D/H in solar system water. We propose this difference arises at least in part due to 1) the availability of additional chemical fractionation pathways for organics beyond that for water, and 2) the higher volatility of key carbon reservoirs compared to oxygen. We test this hypothesis using detailed disk models, including a sophisticated, new disk ionization treatment with a low cosmic ray ionization rate, and find that disk chemistry leads to higher deuterium enrichment in organics compared to water, helped especially by fractionation via the precursors CH$_2$D$^+$/CH$_3^+$. We also find that the D/H ratio in individual species varies significantly depending on their particular formation pathways. For example, from $\sim20-40$ AU, CH$_4$ can reach $\rm{D/H\sim2\times10^{-3}}$, while D/H in CH$_3$OH remains locally unaltered. Finally, while the global organic D/H in our models can reproduce intermediately elevated D/H in the bulk hydrocarbon reservoir, our models are unable to reproduce the most deuterium-enriched organic materials in the solar system, and thus our model requires some inheritance from the cold interstellar medium from which the Sun formed.Comment: 11 pages, 7 figures, accepted for publication in Ap

Lymph node tissue kallikrein-related peptidase 6 mRNA: a progression marker for colorectal cancer

BACKGROUND: A most important characteristic feature for poor prognosis in colorectal cancer (CRC) is the presence of lymph node metastasis. Determination of carcinoembryonic antigen (CEA) mRNA levels in lymph nodes has proven powerful for quantification of disseminated tumour cells. Here, we investigate the utility of human tissue kallikrein-related peptidase 6 (KLK6) mRNA as a progression biomarker to complement CEA mRNA, for improved selection of patients in need of adjuvant therapy and intensified follow-up after surgery. METHODS: Lymph nodes of pTNM stage I-IV CRC-(166 patients/503 lymph nodes) and control (23/108) patients were collected at surgery and analysed by quantitative RT-PCR. RESULTS: Lymph node KLK6 positivity was an indicator of poor outcome (hazard ratio 3.7). Risk of recurrence and cancer death increased with KLK6 lymph node levels. Patients with KLK6 lymph node levels above the 90th percentile had a hazard ratio of 6.5 and 76 months shorter average survival time compared to patients with KLK6 negative nodes. The KLK6 positivity in lymph nodes with few tumour cells, that is, low CEA mRNA levels, also indicated poor prognosis (hazard ratio 2.8). CONCLUSION: In CRC patients, lymph node KLK6 positivity indicated presence of aggressive tumour cells associated with poor prognosis and high risk of tumour recurrence. British Journal of Cancer (2012) 107, 150-157. doi: 10.1038/bjc.2012.220 www.bjcancer.com Published online 14 June 2012 (C) 2012 Cancer Research U

An ALMA Survey of H₂CO in Protoplanetary Disks

H₂CO is one of the most abundant organic molecules in protoplanetary disks and can serve as a precursor to more complex organic chemistry. We present an Atacama Large Millimeter/submillimeter Array survey of H₂CO toward 15 disks covering a range of stellar spectral types, stellar ages, and dust continuum morphologies. H₂CO is detected toward 13 disks and tentatively detected toward a fourteenth. We find both centrally peaked and centrally depressed emission morphologies, and half of the disks show ring-like structures at or beyond expected CO snowline locations. Together these morphologies suggest that H₂CO in disks is commonly produced through both gas-phase and CO-ice-regulated grain-surface chemistry. We extract disk-averaged and azimuthally-averaged H₂CO excitation temperatures and column densities for four disks with multiple H₂CO line detections. The temperatures are between 20–50 K, with the exception of colder temperatures in the DM Tau disk. These temperatures suggest that H₂CO emission in disks generally emerges from the warm molecular layer, with some contributions from the colder midplane. Applying the same H₂CO excitation temperatures to all disks in the survey, we find that H₂CO column densities span almost three orders of magnitude (~5 × 10¹¹–5 × 10¹⁴ cm⁻²). The column densities appear uncorrelated with disk size and stellar age, but Herbig Ae disks may have less H₂CO compared to T Tauri disks, possibly because of less CO freeze-out. More H₂CO observations toward Herbig Ae disks are needed to confirm this tentative trend, and to better constrain under which disk conditions H₂CO and other oxygen-bearing organics efficiently form during planet formation

The Radial Distribution of H_2 and CO in TW Hya as Revealed by Resolved ALMA Observations of CO Isotopologues

CO is widely used as a tracer of molecular gas. However, there is now mounting evidence that gas phase carbon is depleted in the disk around TW Hya. Previous efforts to quantify this depletion have been hampered by uncertainties regarding the radial thermal structure in the disk. Here we present resolved ALMA observations of ^(13)CO 3-2, C^(18)O 3-2, ^(13)CO 6-5, and C^(18)O 6-5 emission in TW Hya, which allow us to derive radial gas temperature and gas surface density profiles, as well as map the CO abundance as a function of radius. These observations provide a measurement of the surface CO snowline at ~30 AU and show evidence for an outer ring of CO emission centered at 53 AU, a feature previously seen only in less abundant species. Further, the derived CO gas temperature profile constrains the freeze out temperature of CO in the warm molecular layer to <21K. Combined with the previous detection of HD 1-0, these data constrain the surface density of the warm H_2 gas in the inner ~30 AU such that Σwarm gas = 4.7^(+3.0)_(-2.9) g cm^(-2)(R/10 au)^(-1/2). We find that CO is depleted by two orders of magnitude from R = 10-60 AU, with the small amount of CO returning to the gas phase inside the surface CO snowline insufficient to explain the overall depletion. Finally, this new data is used in conjunction with previous modeling of the TW Hya disk to constrain the midplane CO snowline to 17–23 AU