We report on absorption measurements of the isotopic composition of water in a demineralized sample by means of wavelength modulation spectroscopy of H2O lines in the spectral region around 2.8μm. The mid-IR radiation was obtained by difference-frequency mixing of the radiation of an extended cavity diode laser (λ=780nm) and that of a diode-pumped monolithic Nd–YAG laser. Preliminary tests indicate the possibility of obtaining a precision for the 18O/16O, 17O/16O and 2H/16O isotope ratio measurements of the order of 1per mil.

We report on the first Doppler-free spectroscopy investigation of an atomic species, xenon, performed in the mid-infrared using difference-frequency radiation. The absorption saturated spectrum of the xenon 6p[3/2]2?5d[5/2]3 transition (2p6?3d'1 in Paschen notation) at 3.1076 microm was investigated using about 60 microwatts of cw narrowband radiation (Deltanu=50 kHz) generated by difference-frequency mixing in a periodically-poled Lithium Niobate crystal. A single frequency Ti:Sapphire laser (power 800 mW) and a monolithic diode-pumped Nd:YAG laser (300 mW) were used as pump and signal waves respectively. We used natural enriched xenon, which contains nine stable isotopes, two of which, 129Xe and 131Xe, exhibit a hyperfine structure owing to their nuclear spin. The small isotope displacements expected for this atom and the complex hyperfine structure of the odd isotopes make it difficult to fully resolve the recorded saturated-absorption spectra. In spite of this, we have been able to analyze the isolated 129Xe F''=5/2?F'=7/2 hyperfine component by means of first-derivative FM spectroscopy.

We detect acetylene and water-vapor lines by using a difference-frequency generator in the spectral region around 3 mm. Both C2H2 and H2O lines belong to fundamental vibrational bands and exhibit a line strength of the order of 10-20 cm/mol. Acetylene molecules were detected either by pure absorption or by first-derivative wavelength-modulation spectroscopy. The minimum detection sensitivity achieved for C2H2 in nitrogen was 4 ppb (parts in 109). Moreover, we discuss the effects of C2H2 pressure reduction in the presence of nitrogen in order to estimate systematic errors in the concentration measurements. Finally, we tested the accuracy of our spectrometer by detecting water vapor present as an impurity in a nitrogen cylinder at a nominal concentration of approximately 5 ppm.