An investigation of possible mechanisms of the water-gas shift reaction over a ZrO2-supported Pt catalyst

The present work investigates the reactivity of the surface species observable by in situ DRIFTS formed over a Pt/ZrO2 during the water-gas shift (WGS) reaction. A DRIFTS cell/mass spectrometer system was operated at the chemical steady state during isotopic transients to yield information about the true nature (i.e., main reaction intermediate or spectators) of adsorbates. Only carbonyl and formate species were observed by DRIFTS under reaction conditions; the surface coverage of carbonate species was negligible. Isotopic transient kinetic analyses revealed that formates exchanged uniformly according to a first-order law, suggesting that most formates observed by DRIFTS were of the same reactivity. In addition, the time scale of the exchange of the reaction product CO2 was significantly shorter than that of the surface formates. Therefore, a formate route based on the formates as detected by DRIFTS can be ruled out as the main reaction pathway in the present case. The number of precursors of the reaction product CO2 was smaller than the number of surface Pt atoms, suggesting that carbonyl species or some \

SpaciMS: spatial and temporal operando resolution of reactions within catalytic monoliths

Monolithic catalysts are widely used as structured catalysts, especially in the abatement of pollutants. Probing what happens inside these monoliths during operation is, therefore, vital for modelling and prediction of the catalyst behavior. SpaciMS is a spatially resolved capillary-inlet mass spectroscopy system allowing for the generation of spatially resolved maps of the reactions within monoliths. In this study SpaciMS results combined with 3D CFD modelling demonstrate that SpaciMS is a highly sensitive and minimally invasive technique that can provide reaction maps as well as catalytic temporal behavior. Herein we illustrate this by examining kinetic oscillations during a CO oxidation reaction over a Pt/Rh on alumina catalyst supported on a cordierite monolith. These oscillations were only observed within the monolith by SpaciMS between 30 and 90% CO conversion. Equivalent experiments performed in a plug-flow reactor using this catalyst in a crushed form over a similar range of reaction conditions did not display any oscillations demonstrating the importance of intra monolith analysis. This work demonstrates that the SpaciMS offers an accurate and comprehensive picture of structured catalysts under operation.

A Transit Timing Analysis of Mine RISE Light Curves of the Exoplanet System TrES-3

We present nine newly observed transits of TrES-3, taken as part of a transit timing program using the RISE instrument on the Liverpool Telescope. A Markov-Chain Monte Carlo analysis was used to determine the planet star radius ratio and inclination of the system, which were found to be R-p/R-star = 0.1664(-0.0018)(+0.0011) and i = 81.73(-0.04)(+0.13), respectively, consistent with previous results. The central transit times and uncertainties were also calculated, using a residual-permutation algorithm as an independent check on the errors. A re-analysis of eight previously published TrES-3 light curves was conducted to determine the transit times and uncertainties using consistent techniques. Whilst the transit times were not found to be in agreement with a linear ephemeris, giving chi(2) = 35.07 for 15 degrees of freedom, we interpret this to be the result of systematics in the light curves rather than a real transit timing variation. This is because the light curves that show the largest deviation from a constant period either have relatively little out-of-transit coverage or have clear systematics. A new ephemeris was calculated using the transit times and was found to be T-c(0) = 2454632.62610 +/- 0.00006 HJD and P = 1.3061864 +/- 0.0000005 days. The transit times were then used to place upper mass limits as a function of the period ratio of a potential perturbing planet, showing that our data are sufficiently sensitive to have probed sub-Earth mass planets in both interior and exterior 2:1 resonances, assuming that the additional planet is in an initially circular orbit.

A transit timing analysis of seven RISE light curves of the exoplanet system HAT-P-3

We present seven light curves of the exoplanet system HAT-P-3, taken as part of a transit timing programme using the rapid imager to search for exoplanets instrument on the Liverpool Telescope. The light curves are analysed using a Markov chain Monte Carlo algorithm to update the parameters of the system. The inclination is found to be i = 86.75+0.22-0.21°, the planet-star radius ratio to be Rp/R* = 0.1098+0.0010-0.0012 and the stellar radius to be R* = 0.834+0.018-0.026Rsolar, consistent with previous results but with a significant improvement in the precision. Central transit times and uncertainties for each light curve are also determined, and a residual permutation algorithm is used as an independent check on the errors. The transit times are found to be consistent with a linear ephemeris, and a new ephemeris is calculated as Tc(0) = 2454856.70118 +/- 0.00018 HJD and P = 2.899738 +/- 0.000007 d. Model timing residuals are fitted to the measured timing residuals to place upper mass limits for a hypothetical perturbing planet as a function of the period ratio. These show that we have probed for planets with masses as low as 0.33 and 1.81 M? in the interior and exterior 2:1 resonances, respectively, assuming the planets are initially in circular orbits.

WASP-34b: a near-grazing transiting sub-Jupiter-mass exoplanet in a hierarchical triple system

We report the discovery of WASP-34b, a sub-Jupiter-mass exoplanet transiting its 10.4-magnitude solar-type host star (1SWASP J110135.89-235138.4; TYC 6636-540-1) every 4.3177 days in a slightly eccentric orbit (e = 0.038±0.012). We find a planetary mass of 0.59±0.01 MJup and radius of 1.22-0.08+0.11 RJup. There is a linear trend in the radial velocities of 55±4 m s-1 y-1 indicating the presence of a long-period third body in the system with a mass ?0.45 MJup at a distance of ?1.2 AU from the host star. This third-body is either a low-mass star, a white dwarf, or another planet. The transit depth ((RP/Rstar)2 = 0.0126) and high impact parameter (b = 0.90) suggest that this could be the first known transiting exoplanet expected to undergo grazing transits, but with a confidence of only 80%. Radial velocity and photometric data are only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/526/A130

Wasp-7: A Bright Transiting-Exoplanet System in the Southern Hemisphere

We report that a Jupiter-mass planet, WASP-7b, transits the V = 9.5 star HD 197286 every 4.95 d. This is the brightest discovery from the WASP-South transit survey so far and is currently the brightest transiting-exoplanet system in the southern hemisphere. WASP-7b is among the densest of the known Jupiter-mass planets, suggesting that it has a massive core. The planet mass is 0.96+0.12 -0.18 M Jup, the radius is 0.915+0.046 -0.040 R Jup, and the density is 1.26+0.25 -0.21 ?Jup (1.67+0.33 -0.28 g cm-3).

WASP-22 b: A Transiting "Hot Jupiter" Planet in a Hierarchical Triple System

We report the discovery of a transiting planet orbiting the star TYC 6446-326-1. The star, WASP-22, is a moderately bright (V = 12.0) solar-type star (Teff = 6000 ± 100 K, [Fe/H] = -0.05 ± 0.08). The light curve of the star obtained with the WASP-South instrument shows periodic transit-like features with a depth of about 1% and a duration of 0.14 days. The presence of a transit-like feature in the light curve is confirmed using z-band photometry obtained with Faulkes Telescope South. High-resolution spectroscopy obtained with the CORALIE and HARPS spectrographs confirms the presence of a planetary mass companion with an orbital period of 3.533 days in a near-circular orbit. From a combined analysis of the spectroscopic and photometric data assuming that the star is a typical main-sequence star we estimate that the planet has a mass M p = 0.56 ± 0.02M Jup and a radius R p = 1.12 ± 0.04R Jup. In addition, there is a linear trend of 40 m s-1 yr-1 in the radial velocities measured over 16 months, from which we infer the presence of a third body with a long-period orbit in this system. The companion may be a low mass M-dwarf, a white dwarf, or a second planet.

Eclipsing Binary Science via the Merging of Transit and Doppler Exoplanet Survey Data—A Case Study with the MARVELS Pilot Project and SuperWASP

Exoplanet transit and Doppler surveys discover many binary stars during their operation that can be used to conduct a variety of ancillary science. Specifically, eclipsing binary stars can be used to study the stellar mass-radius relationship and to test predictions of theoretical stellar evolution models. By cross-referencing 24 binary stars found in the MARVELS Pilot Project with SuperWASP photometry, we find two new eclipsing binaries, TYC 0272-00458-1 and TYC 1422-01328-1, which we use as case studies to develop a general approach to eclipsing binaries in survey data. TYC 0272-00458-1 is a single-lined spectroscopic binary for which we calculate a mass of the secondary and radii for both components using reasonable constraints on the primary mass through several different techniques. For a primary mass of M 1 = 0.92 ± 0.1 M sun, we find M 2 = 0.610 ± 0.036 M sun, R 1 = 0.932 ± 0.076 R sun, and R 2 = 0.559 ± 0.102 R sun, and find that both stars have masses and radii consistent with model predictions. TYC 1422-01328-1 is a triple-component system for which we can directly measure the masses and radii of the eclipsing pair. We find that the eclipsing pair consists of an evolved primary star (M 1 = 1.163 ± 0.034 M sun, R 1 = 2.063 ± 0.058 R sun) and a G-type dwarf secondary (M 2 = 0.905 ± 0.067 M sun, R 2 = 0.887 ± 0.037 R sun). We provide the framework necessary to apply this analysis to much larger data sets.

A lower mass for the exoplanet WASP-21b

We present high-precision transit observations of the exoplanet WASP-21b, obtained with the Rapid Imager to Search for Exoplanets instrument mounted on the 2.0-m Liverpool Telescope. A transit model is fitted, coupled with a Markov chain Monte Carlo routine, to derive accurate system parameters. The two new high-precision transits allow us to estimate the stellar density directly from the light curve. Our analysis suggests that WASP-21 is evolving off the main sequence which led to a previous overestimation of the stellar density. Using isochrone interpolation, we find a stellar mass of 0.86 ± 0.04 Msun, which is significantly lower than previously reported (1.01 ± 0.03 Msun). Consequently, we find a lower planetary mass of 0.27 ± 0.01 MJup. A lower inclination (87?4 ± 0?3) is also found for the system than previously reported, resulting in a slightly larger stellar (R*= 1.10 ± 0.03 Rsun) and planetary radius (Rp= 1.14 ± 0.04 RJup). The planet radius suggests a hydrogen/helium composition with no core which strengthens the correlation between planetary density and host star metallicity. A new ephemeris is determined for the system, i.e. T0= 245 5084.519 74 ± 0.000 20 (HJD) and P= 4.322 5060 ± 0.000 0031 d. We found no transit timing variations in WASP-21b.

High-precision transit observations of the exoplanet WASP-13b with the RISE instrument

WASP-13b is a sub-Jupiter mass exoplanet orbiting a G1V type star with a period of 4.35 d.The current uncertainty in its impact parameter (0 < b < 0.46) results in poorly definedstellar and planetary radii. To better constrain the impact parameter, we have obtained highprecisiontransit observations with the rapid imager to search for exoplanets (RISE) instrumentmounted on 2.0-m Liverpool Telescope. We present four new transits which are fitted witha Markov chain Monte Carlo routine to derive accurate system parameters. We found anorbital inclination of 85. ◦ 2 ± 0. ◦ 3 resulting in stellar and planetary radii of 1.56 ± 0.04 Rand 1.39 ± 0.05RJup, respectively. This suggests that the host star has evolved off the mainsequence and is in the hydrogen-shell-burning phase.We also discuss how the limb darkeningaffects the derived system parameters.With a density of 0.17ρJ,WASP-13b joins the group oflow-density planets whose radii are too large to be explained by standard irradiation models.We derive a new ephemeris for the system, T0 = 245 5575.5136 ± 0.0016 (HJD) and P =4.353 011 ± 0.000 013 d. The planet equilibrium temperature (Tequ = 1500 K) and the brighthost star (V = 10.4mag) make it a good candidate for follow-up atmospheric studies.

The Kepler-10 Planetary System Revisited by HARPS-N: A Hot Rocky World and a Solid Neptune-Mass Planet

Kepler-10b was the first rocky planet detected by the Kepler satellite and confirmed with radial velocity follow-up observations from Keck-HIRES. The mass of the planet was measured with a precision of around 30%, which was
insufficient to constrain models of its internal structure and composition in detail. In addition to Kepler-10b, a second planet transiting the same star with a period of 45 days was statistically validated, but the radial velocities were only
good enough to set an upper limit of 20 M⊕ for the mass of Kepler-10c. To improve the precision on the mass for planet b, the HARPS-N Collaboration decided to observe Kepler-10 intensively with the HARPS-N spectrograph
on the Telescopio Nazionale Galileo on La Palma. In total, 148 high-quality radial-velocity measurements were obtained over two observing seasons. These new data allow us to improve the precision of the mass determination for Kepler-10b to 15%. With a mass of 3.33 ± 0.49 M⊕ and an updated radius of 1.47+0.03 −0.02 R⊕, Kepler-10b has a density of 5.8 ± 0.8 g cm−3, very close to the value predicted by models with the same internal structure and composition as the Earth. We were also able to determine a mass for the 45-day period planet Kepler-10c, with an even better precision of 11%. With a mass of 17.2 ± 1.9 M⊕ and radius of 2.35+0.09 −0.04 R⊕, Kepler-10c has a density of 7.1 ± 1.0 g cm−3. Kepler-10c appears to be the first strong evidence of a class of more massive solid planets with longer orbital periods

Characterization of the Kepler-101 planetary system with HARPS-N. A hot super-Neptune with an Earth-sized low-mass companion

We characterize the planetary system Kepler-101 by performing a combined differential evolution Markov chain Monte Carlo analysisof Kepler data and forty radial velocities obtained with the HARPS-N spectrograph. This system was previously validated and iscomposed of a hot super-Neptune, Kepler-101b, and an Earth-sized planet, Kepler-101c. These two planets orbit the slightly evolvedand metal-rich G-type star in 3.49 and 6.03 days, respectively. With mass Mp = 51.1+5.1−4.7 M⊕, radius Rp = 5.77+0.85−0.79 R⊕, and density ρp = 1.45+0.83 −0.48 g cm−3, Kepler-101b is the first fully characterized super-Neptune, and its density suggests that heavy elements makeup a significant fraction of its interior; more than 60% of its total mass. Kepler-101c has a radius of 1.25+0.19−0.17 R⊕, which implies theabsence of any H/He envelope, but its mass could not be determined because of the relative faintness of the parent star for highly precise radial-velocity measurements (Kp = 13.8) and the limited number of radial velocities. The 1σ upper limit, Mp < 3.8 M⊕, excludes a pure iron composition with a probability of 68.3%. The architecture of the planetary system Kepler-101 − containing aclose-in giant planet and an outer Earth-sized planet with a period ratio slightly larger than the 3:2 resonance − is certainly of interest for scenarios of planet formation and evolution. This system does not follow the previously reported trend that the larger planet has the longer period in the majority of Kepler systems of planet pairs with at least one Neptune-sized or larger planet.

X-ray driven evaporation of exoplanet atmospheres: discovery of a uniquely suited test system

The evaporation of exoplanetary atmospheres is thought to be driven by high-energy irradiation. However, the actual mass loss rates are not well constrained. Co-I Kipping has recently discovered that the star KOI-314, an M1V dwarf at 65 pc distance, is orbited by two earth-sized planets, the inner one of them rocky and the outer one gaseous (P_orb = 14d and 23d). Other recent works have shown an abundance of small rocky planets in very close orbits around their host stars, suggesting that the stellar high-energy irradiation evaporates away gaseous envelopes. KOI-314 is the first nearby system in which earth-sized planets of both types are detected, allowing us to constrain the efficiency of planetary evaporation if the stellar X-ray irradiation is measured. We therefore propose a 10 ks Chandra ACIS-S pointing to determine the stellar X-ray luminosity and hardness ratio. The accuracy of the orbital solution decreases quickly due to Transit-Timing Variations, which is why we ask for DDT.

The HARPS-N Rocky Planet Search. I. HD 219134 b: A transiting rocky planet in a multi-planet system at 6.5 pc from the Sun

We know now from radial velocity surveys and transit space missions thatplanets only a few times more massive than our Earth are frequent aroundsolar-type stars. Fundamental questions about their formation history,physical properties, internal structure, and atmosphere composition are,however, still to be solved. We present here the detection of a systemof four low-mass planets around the bright (V = 5.5) and close-by (6.5pc) star HD 219134. This is the first result of the Rocky Planet Searchprogramme with HARPS-N on the Telescopio Nazionale Galileo in La Palma.The inner planet orbits the star in 3.0935 ± 0.0003 days, on aquasi-circular orbit with a semi-major axis of 0.0382 ± 0.0003AU. Spitzer observations allowed us to detect the transit of the planetin front of the star making HD 219134 b the nearest known transitingplanet to date. From the amplitude of the radial velocity variation(2.25 ± 0.22 ms-1) and observed depth of the transit(359 ± 38 ppm), the planet mass and radius are estimated to be4.36 ± 0.44 M⊕ and 1.606 ± 0.086R⊕, leading to a mean density of 5.76 ± 1.09 gcm-3, suggesting a rocky composition. One additional planetwith minimum-mass of 2.78 ± 0.65 M⊕ moves on aclose-in, quasi-circular orbit with a period of 6.767 ± 0.004days. The third planet in the system has a period of 46.66 ± 0.08days and a minimum-mass of 8.94 ± 1.13 M⊕, at0.233 ± 0.002 AU from the star. Its eccentricity is 0.46 ±0.11. The period of this planet is close to the rotational period of thestar estimated from variations of activity indicators (42.3 ± 0.1days). The planetary origin of the signal is, however, thepreferredsolution as no indication of variation at the corresponding frequency isobserved for activity-sensitive parameters. Finally, a fourth additionallonger-period planet of mass of 71 M⊕ orbits the starin 1842 days, on an eccentric orbit (e = 0.34 ± 0.17) at adistance of 2.56 AU.The photometric time series and radial velocities used in this work areavailable in electronic form at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr(ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/584/A72

Identification of an unknown b-agonist in feed by liquid chromatography/bioassay/quadrupole time-of-flight tandem mass spectrometry with accurate mass measurement.

A new approach to the search for residues of unknown growth promoting agents such as anabolic steroids and -agonists in feed is presented. Following primary extraction and clean-up, samples are separated using gradient liquid chromatography (LC). The effluent is split towards two identical 96-well fraction collectors and an optional electrospray quadrupole time-of-flight mass spectrometry (QTOFMS) system for accurate mass measurement. One 96-well plate is used for a bioassay (enzyme-immuno assay, receptor assay) and will detect the bioactivity and position of the relevant peak in the chromatogram. The positive well in the second 96-well plate is used for identification by LC/QTOFMS/MS. The value of this LC/bioassay/QTOFMS/MS methodology is highlighted by the finding and structure elucidation of a new -agonist in a feed extract.