We have constructed a cavity ring-down spectrometer employing a near-IR external cavity diode laser capable of measuring 13C/12C isotopic ratios in CO2 in human breath. The system, which has a demonstrated minimum detectable absorption loss of 3.2 x 10(-11) cm(-1) Hz(-1/2), determines the isotopic ratio of 13C16O16O/12C16O16O by measuring the intensities of rotationally resolved absorption features of each species. As in isotope ratio mass spectrometry (IRMS), the isotopic ratio of a sample is compared to that of a standard CO2 sample calibrated to the Pee Dee Belemnite scale and reported as the sample's delta13C value. Measurements of eight replicate CO2 samples standardized by IRMS and consisting of 5% CO2 in N2 at atmospheric pressure demonstrated a precision of 0.22/1000 for the technique. Delta13C values were also obtained for breath samples from individuals testing positive and negative for the presence of Helicobacter pylori, the leading cause of peptic ulcers in humans. This study demonstrates the ability of the instrument to obtain delta13C values in breath samples with sufficient precision to serve as a useful medical diagnostic.

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Infrared cavity ringdown laser absorption spectroscopy has been used to study the O-H stretching vibrations of jet-cooled methanol clusters in direct absorption. Rovibrational bands for (CH 3 OH) 2 , (CH 3 OH) 3 , and (CH 3 OH) 4 have been measured. Both bonded and free O-H stretches were measured for the dimer, indicating that its structure is linear. Five bands were assigned to the methanol trimer, indicating the presence of a second cyclic isomer in the molecular beam. A detailed study of the free O-H stretching region shows that methanol clusters larger than dimer must exist in cyclic ring configurations. In order to facilitate spectral assignment, harmonic frequencies and infrared intensities were calculated for the methanol monomer, dimer, and trimer with second order Mo "ller-Plesset perturbation theory. Using the theoretical infrared intensities and measured vibrational band absorptions, absolute cluster concentrations were calculated. Results agree with previous experimental and theoretical work.

We report the first measurement of water monomer bending vibrations in gaseous (H2O) n clusters. Infrared cavity ringdown spectroscopy reveals discrete and sequentially blue-shifted bands near 6 μm for n = 2−4 and unresolved broad features for n > 4, supporting both theoretical predictions and solid-state spectroscopy results. These measurements provide a measure of the monomer distortion that accompanies sequential hydrogen bond formation, which will be valuable for the construction of potential energy surfaces for describing water.

Understanding the processes that control the terrestrial exchange of carbon is critical for assessing atmospheric CO2 budgets. Carbonyl sulfide (COS) is taken up by vegetation during photosynthesis following a pathway that mirrors CO2 but has a small or nonexistent emission component, providing a possible tracer for gross primary production. Field measurements of COS and CO2 mixing ratios were made in forest, senescent grassland, and riparian ecosystems using a laser absorption spectrometer installed in a mobile trailer. Measurements of leaf fluxes with a branch‐bag gas‐exchange system were made across species from 10 genera of trees, and soil fluxes were measured with a flow‐through chamber. These data show (1) the existence of a narrow normalized daytime uptake ratio of COS to CO2 across vascular plant species of 1.7, providing critical information for the application of COS to estimate photosynthetic CO2 fluxes and (2) a temperature‐dependent normalized uptake ratio of COS to CO2 from soils. Significant nighttime uptake of COS was observed in broad‐leafed species and revealed active stomatal opening prior to sunrise. Continuous high‐resolution joint measurements of COS and CO2 concentrations in the boundary layer are used here alongside the flux measurements to partition the influence that leaf and soil fluxes and entrainment of air from above have on the surface carbon budget. The results provide a number of critical constraints on the processes that control surface COS exchange, which can be used to diagnose the robustness of global models that are beginning to use COS to constrain terrestrial carbon exchange.