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The exclusive use of carbonate reference materials is a robust method for the standardization of clumped isotope measurements • Measurements using different acid temperatures, designs of preparation lines, and mass spectrometers are statistically indistinguishable • We propose new consensus values for a set of 7 carbonate reference materials and updated guidelines to report clumped isotope measurements

Recent infrared spectroscopy of hot exoplanets is beginning to reveal their atmospheric composition. Deep within the planetary atmosphere, the composition is controlled by thermochemical equilibrium. Photochemistry becomes important higher in the atmosphere, at levels above ∼1 bar. These two chemistries compete between ∼1 and 10 bars in hot-Jupiter-like atmospheres, depending on the strength of the eddy mixing and temperature. HD 189733b provides an excellent laboratory in which to study the consequences of chemistry of hot atmospheres. The recent spectra of HD 189733b contain signatures of CH 4 , CO 2 , CO, and H 2 O. Here we identify the primary chemical pathways that govern the abundances of CH 4 , CO 2 , CO, and H 2 O in the cases of thermochemical equilibrium chemistry, photochemistry, and their combination. Our results suggest that the disequilibrium mechanisms can significantly enhance the abundances of these species above their thermochemical equilibrium value, so some caution must be taken when assuming that an atmosphere is in strict thermochemical equilibrium.

Atomic hydrogen loss at the top of HD 209458b's atmosphere has been recently detected Vidal-Madjar et al. 2003. We have developed a 1-dimensional model to study the chemistry in the upper atmosphere of this extrasolar "hot jupiter". The 3 most abundant elements (other than He), as well as 4 parent molecules are included in this model, viz., H, C, O, H2, CO, H2O, and CH4. The higher temperatures (~ 1000 K) and higher stellar irradiance (~6x10^5 W m^{-2}) strongly enhance and modify the chemical reaction rates in this atmosphere. Our two main results are that (a) the production of atomic hydrogen in the atmosphere is mainly driven by H2O photolysis and reaction of OH with H2, and is not sensitive to the exact abundances of CO, H2O, and CH4, and (b) H2O and CH4 can be produced via the photolysis of CO followed by the reactions with H2.Comment: submitted to ApJ

The study reveals that for future research on N2O isotopocules, standardisation against N2O reference material is essential to improve interlaboratory compatibility. For atmospheric monitoring activities, we suggest N2O in whole air as a unifying scale anchor.

[1] We present a kinetic calculation for the isotopic composition of stratospheric ozone. The calculated enrichments of 49 O 3 and 50 O 3 are in agreement with atmospheric measurements made at midlatitudes. Integrating the kinetic fractionation processes in the formation and photolysis of ozone, we obtain enrichments of $7.5-10.5 and $7.5-12.5% (referenced to atmospheric O 2 ) for d O 3 and d50 O 3 , respectively, at altitudes between 20 and 35 km; the photolysis in the Hartley band of ozone is responsible for the observed altitude variation. The overall magnitude of the ozone enrichments ($10%) is large compared with that commonly known in atmospheric chemistry and geochemistry. The heavy oxygen atom in ozone is therefore useful as a tracer of chemical species and pathways that involve ozone or its derived products. For example, the mass anomalies of oxygen in two greenhouse gases, CO 2 and N 2 O, are likely the consequences of the transfer of heavy oxygen atoms from ozone.