Optical-feedback cavity-enhanced absorption spectroscopy is demonstrated in the mid-IR by using a quantum cascade laser (emitting at 4.46 μm). The laser linewidth reduction and frequency locking by selective optical feedback from the resonant cavity field turns out to be particularly advantageous in this spectral range: It allows strong cavity transmission, which compensates for low light sensitivity, especially when using room-temperature detectors. We obtain a noise equivalent absorption coefficient of 3 × 10(-9)/cm for 1 s averaging of spectra composed by 100 independent points. At 4.46 μm, this yields a detection limit of 35 parts in 10(12) by volume for N(2)O at 50 mbar, corresponding to 4 × 10(7) molecules/cm(3), or still to 1 fmol in the sample volume.

A global chemistry transport model is employed to investigate the impact of recent laboratory determinations of photolysis parameters for formaldehyde on concentrations of tropospheric trace gases. Using the new laboratory data, the photolysis of formaldehyde is a more significant removal pathway. HO x levels are increased with the greatest changes towards the top of the troposphere and the poles, making formaldehyde a more significant source of upper tropospheric HO x than previously thought. Global totals of ozone and secondary organic aerosol increase with the rise in ozone being more significant at higher solar zenith angles.

Absolute quantum yields for the radical (H + HCO) channel of HCHO photolysis, Phi(HCO), have been measured for the tropospherically relevant range of wavelengths (lambda) between 300 and 330 nm. The HCO photoproduct was directly detected by using a custom-built, combined ultra-violet (UV) absorption and cavity ring down (CRD) detection spectrometer. This instrument was previously employed for high-resolution (spectral resolution approximately 0.0035 nm) measurements of absorption cross-sections of HCHO, sigma(HCHO)(lambda), and relative HCO quantum yields. Absolute Phi(HCO) values were measured at seven wavelengths, lambda = 303.70, 305.13, 308.87, 314.31, 320.67, 325.59, and 329.51 nm, using an independent calibration technique based on the simultaneous UV photolysis of HCHO and Cl(2). These Phi(HCO) measurements display greater variability as a function of wavelength than the current NASA-JPL recommendations for Phi(HCO). The absolute Phi(HCO)(lambda) determinations and previously measured sigma(HCHO)(lambda) were used to scale an extensive set of relative HCO yield measurements. The outcome of this procedure is a full suite of data for the product of the absolute radical quantum yield and HCHO absorption cross-section, Phi(HCO)(lambda)sigma(HCHO)(lambda), at wavelengths from 302.6 to 331.0 nm with a wavelength resolution of 0.005 nm. This product of photochemical parameters is combined with high-resolution solar photon flux data to calculate the integrated photolysis rate of HCHO to the radical (H + HCO) channel, J(HCO). Comparison with the latest NASA-JPL recommendations, reported at 1 nm wavelength resolution, suggests an increased J(HCO) of 25% at 0 degrees solar zenith angle (SZA) increasing to 33% at high SZA (80 degrees). The differences in the calculated photolysis rate compared with the current HCHO data arise, in part, from the higher wavelength resolution of the current data set and highlight the importance of using high-resolution spectroscopic techniques to achieve a complete and accurate picture of HCHO photodissociation processes. All experimental Phi(HCO)(lambda)sigma(HCHO)(lambda) data are available for the wavelength range 302.6-331.0 nm (at 294 and 245 K and under 200 Torr of N(2) bath gas) as Supporting Information with wavelength resolutions of 0.005, 0.1, and 1.0 nm. Equivalent data sets of Phi(H(2)+CO)(lambda)sigma(HCHO)(lambda) for the molecular (H(2) + CO) photofragmentation channel, produced using the measured Phi(HCO)(lambda) sigma(HCHO)(tau) values, are also provided at 0.1 and 1.0 nm resolution.

Quantum yields, Phi(NO(2)), are reported for the NO(2) formation channel (RO + NO(2)) following photodissociation of methyl and isopropyl nitrate (CH(3)ONO(2) and C(3)H(7)ONO(2)) at the tropospherically relevant wavelengths of 308-320 nm. Measurements were made using ultra-violet (UV) laser absorption and cavity ring down spectroscopy (CRDS) detection of the NO(2) photoproducts. Analysis of CRDS data to obtain NO(2) quantum yields required account to be taken of the spatially inhomogeneous NO(2) distribution resulting from photolysis with a laser beam with a Gaussian intensity profile. Photodissociation quantum yields were measured to be unity (with