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Photofragmentation spectroscopy is combined with tunable diode laser absorption spectroscopy to measure the line shape of the fragment species. This provides flexibility in choosing the UV pulse location within the line shape and accurate quantification of both target species and background fragment concentrations, even under optically thick conditions. The technique is demonstrated by detection of potassium hydroxide (KOH) and atomic potassium K(g) above solid KOH converted in a premixed methane-air flat flame. Time series of KOH(g) and K(g) concentrations are recorded as a function of solid KOH mass and flame stoichiometry. The total substance released during the conversion is in good agreement with the initial solid KOH mass. Under fuel-rich conditions, increased K(g) concentrations at the expense of KOH(g) are observed compared to thermodynamic equilibrium.

A sensitive high-resolution sub-Doppler detecting spectrometer, based on noise-immune cavity-enhanced optical heterodyne molecular spectrometry (NICE-OHMS), for trace gas detection of species whose transitions have severe spectral overlap with abundant concomitant species is presented. It is designed around a NICE-OHMS instrumentation utilizing balanced detection that provides shot-noise limited Doppler-broadened (Db) detection. By synchronous dithering the positions of the two cavity mirrors, the effect of residual etalons between the cavity and other surfaces in the system could be reduced. An Allan deviation of the absorption coefficient of 2.2 × 10−13 cm−1 at 60 s, which, for the targeted transition in C2H2, corresponds to a 3σ detection sensitivity of 130 ppt, is demonstrated. It is shown that despite significant spectral interference from CO2 at the targeted transition, which precludes Db detection of C2H2, acetylene could be detected in exhaled breath of healthy smokers.

We use broadband near-infrared continuous-filtering Vernier spectroscopy (CF-VS) for time-resolved detection of H2O and OH radical in a premixed CH4/air flat flame. The CF-VS spectrometer is based on a femtosecond Er:fiber laser, an external cavity that contains the flame, and a detection system comprising a rotating diffraction grating and photodetectors. Spectra of H2O and OH radical around 1570 nm are continuously recorded with 6.6 GHz spectral resolution, 4.0 × 10−7 cm−1 absorption sensitivity, and 25 ms time resolution, while the fuel-air equivalence ratio is periodically modulated with a square wave. The concentrations of the two analytes are retrieved with percent level precision by a fit of a Vernier model to each spectrum spanning 13 nm. The temporal profiles of both concentrations in each modulation cycle are repeatable and the steady-state concentration levels are in good agreement with predictions based on one-dimensional simulations of a static flat flame. The robust CF-VS spectrometer opens up for quantitative monitoring of multiple products of time-varying combustion processes with relatively simple data acquisition procedures.

Absorption spectroscopy is attractive for combustion diagnostics because it allows in-situ and calibration-free quantification of reactants/products and thermometry. However, spectra measured at atmospheric pressure in the near-infrared telecom range, where laser sources and optical components are readily available, suffer from strong water interference. Cavity-enhanced optical frequency comb spectroscopy (CE-OFCS) is well suited for detection of other species, as it provides broad bandwidth with high signal-to-noise ratio and resolution, and allows de-convolving the spectra hidden among water transitions. Here we report detection of OH in the presence of H2O in an atmospheric premixed methane/air flat flame by CE-OFCS at 1.57 μm. We demonstrate a new water line list that is more accurate than HITEMP [1] and we isolate the OH lines by dividing spectra taken at different heights above the burner (HABs) to retrieve OH concentration and flame temperature.

We present a compact sensor for carbon monoxide (CO) in air and exhaled breath based on a room temperature interband cascade laser (ICL) operating at 4.69 µm, a low-volume circular multipass cell and wavelength modulation absorption spectroscopy. A fringe-limited (1σ) sensitivity of 6.5 × 10−8 cm−1Hz-1/2 and a detection limit of 9 ± 5 ppbv at 0.07 s acquisition time are achieved, which constitutes a 25-fold improvement compared to direct absorption spectroscopy. Integration over 10 s increases the precision to 0.6 ppbv. The setup also allows measuring the stable isotope 13CO in breath. We demonstrate quantification of indoor air CO and real-time detection of CO expirograms from healthy non-smokers and a healthy smoker before and after smoking. Isotope ratio analysis indicates depletion of 13CO in breath compared to natural abundance.

We report broadband detection of OH in a premixed CH4/air flat flame at atmospheric pressure using cavity-enhanced absorption spectroscopy based on an Er:fiber femtosecond laserand a Fourier transform spectrometer.By taking ratios of spectra measured at different heights above the burner we separate twenty OH transitions from the largely overlapping water background. Weretrieve from fits to the OH lines the relative variation of the OH concentration and flame temperature with height above the burner and compare them with 1-D simulations of the flamestructure. Full Text: PDF ReferencesG. Meijer, M. G. Boogaarts, R. T. Jongma, D. H. Parker and A. M. Wodtke, "Coherent cavity ring down spectroscopy", Chem. Phys. Lett. 217, 1, 112 (1994). CrossRef S. Cheskis, I. Derzy, V. A. Lozovsky, A. Kachanov and D. Romanini, "Cavity ring-down spectroscopy of OH radicals in low pressure flame", Appl. Phys. B 66, 3, 377 (1998). CrossRef X. Mercier, E. Therssen, J. F. Pauwels and P. Desgroux, "Cavity ring-down measurements of OH radical in atmospheric premixed and diffusion flames.: A comparison with laser-induced fluorescence and direct laser absorption", Chem. Phys. Lett. 299, 1, 75 (1999). CrossRef J. Scherer, D. Voelkel and D. Rakestraw, "Infrared cavity ringdown laser absorption spectroscopy (IR-CRLAS) in low pressure flames", Appl. Phys. B 64, 6, 699 (1997). CrossRef R. Peeters, G. Berden and G. Meijer, "Near-infrared cavity enhanced absorption spectroscopy of hot water and OH in an oven and in flames", Appl. Phys. B 73, 1, 65 (2001). CrossRef T. Aizawa, "Diode-laser wavelength-modulation absorption spectroscopy for quantitative in situ measurements of temperature and OH radical concentration in combustion gases", Appl. Opt. 40, 27, 4894 (2001). CrossRef B. Löhden, S. Kuznetsova, K. Sengstock, V. M. Baev, et al., "Fiber laser intracavity absorption spectroscopy for in situ multicomponent gas analysis in the atmosphere and combustion environments", Appl. Phys. B 102, 2, 331 (2011). CrossRef A. Matynia, M. Idir, J. Molet, C. Roche, et al., "Absolute OH concentration profiles measurements in high pressure counterflow flames by coupling LIF, PLIF, and absorption techniques", Appl. Phys. B 108, 2, 393 (2012). CrossRef R. S. Watt, T. Laurila, C. F. Kaminski and J. Hult, "Cavity Enhanced Spectroscopy of High-Temperature H2O in the Near-Infrared Using a Supercontinuum Light Source", Appl. Spectrosc. 63, 12, 1389 (2009). CrossRef C. Abd Alrahman, A. Khodabakhsh, F. M. Schmidt, Z. Qu and A. Foltynowicz, "Cavity-enhanced optical frequency comb spectroscopy of high-temperature H2O in a flame", Opt. Express 22, 11, 13889 (2014). CrossRef A. Foltynowicz, P. Maslowski, A. J. Fleisher, B. J. Bjork and J. Ye, "Cavity-enhanced optical frequency comb spectroscopy in the mid-infrared application to trace detection of hydrogen peroxide", Appl. Phys. B 110, 2, 163 (2013). CrossRef Z. Qu, R. Ghorbani, D. Valiev and F. M. Schmidt, "Calibration-free scanned wavelength modulation spectroscopy ? application to H2O and temperature sensing in flames", Opt. Express 23, 12, 16492 (2015). CrossRef L. Rutkowski, A. Khodabakhsh, A. C. Johansson, D. M. Valiev, et al., "Measurement of H2O and OH in a Flame by Optical Frequency Comb Spectroscopy", CLEO: Science and Innovations SW4H.8 (2016). CrossRef L. S. Rothman, I. E. Gordon, Y. Babikov, A. Barbe, et al., "The HITRAN2012 molecular spectroscopic database", J. Quant. Spectrosc. Radiat. Transf. 130, 4 (2013). CrossRef

Using Fourier transform-based cavity-enhanced optical frequency comb spectroscopy around 1.57 µm we measure high precision low pressure spectra of the 3ν1+ ν3 band of CO2 and high temperature H2O and OH spectra in a premixed methane/air flat flame.

Dual-frequency modulation (DFM) has been used to continuously track the frequency shifts of optical cavity modes in the vicinity of an optical transition of a gas inside the cavity for assessment o ...

We demonstrate detection of broadband high-temperature water spectra in a laminar, premixed methane/air flat flame using high-resolution near-infrared cavity-enhanced optical frequency comb spectroscopy incorporating a fast-scanning Fourier transform spectrometer.

This work examines absorption spectrometry by narrowband light in gaseous media with arbitrary optical thickness when the light induces optical saturation or optical pumping. Two quantities are defined: the observed absorbance, Aobs, and the true absorbance, Atrue. The former is the absorbance that is measured under the existing conditions, whereas the latter represents the absorbance one would measure if the light acted solely as a probe of the populations of the various levels, and it is therefore directly proportional to the concentration or density of absorbers. A general integral equation for the propagation of light in media of arbitrary optical thickness in which the light influences the populations of the levels involved is derived. This expression is transcendental in the observed absorbance and cannot be solved analytically. It is shown that an analytical expression can be derived by investigating the inverse relationship, i.e., Atrue = f ( Aobs). Inasmuch as collision and Doppler broadened media react differently to optical saturation, they are considered separately. It is shown that a nonlinear response results if the medium is optically saturated (or pumped) and not optically thin. Expressions for the error introduced if the technique of standard additions is uncritically applied to such a system are derived.

A new diode laser-based double modulation absorption spectrometry (DMAS) technique for detection of species in trace amounts/concentrations is presented. The new technique makes use of a simultaneo ...

Diode laser-based continuous wave cavity ring-down spectroscopy (cw-CRDS) in the near-infrared region has been used to measure the mixing ratio of acetylene (C(2)H(2)) in ambient air. Detection limits of 120 parts per trillion by volume (pptv) for 20 min and 340 pptv for 70 s acquisition time were achieved without sample pre-concentration, measuring on a C(2)H(2) absorption line at 6565.620 cm(-1) (similar to 1523 nm). Several indoor and outdoor air samples were collected at different locations in the Helsinki metropolitan area and analyzed using static-cell measurements. In addition, flow measurements of indoor and outdoor air have been performed continuously over several days with a time resolution of down to one minute. Baseline acetylene levels in the range of 0.4 to 3 parts per billion by volume (ppbv), with a maximum around midday and a minimum during the night, were measured. Sudden high mixing ratios of up to 60 ppbv were observed in outdoor air during daytime on a minute time scale. In general, the indoor mixing ratios were found to be higher than those in outdoor air. The acetylene levels correlated with the ambient CO levels and with outdoor temperature. 678VQ Times Cited:4 Cited References Count:36

As a result of a combination of an external cavity and modulation techniques, noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) is one of the most sensitive absorpt ...

A compact NICE-OHMS spectrometer based on a narrowband fiber laser has been used for detection of C2H2down to an integrated absorption of 5×10-11cm-1in Doppler-broadened and 3×10-10cm-1in Doppler-free mode of operation.

We demonstrate near-infrared cavity-enhanced optical frequency comb spectroscopy of water in a premixed methane/air flat flame. The detection system is based on an Er:fiber femtosecond laser, a high finesse optical cavity containing the flame, and a fast-scanning Fourier transform spectrometer (FTS). High absorption sensitivity is obtained by the combination of a high-bandwidth two-point comb-cavity lock and auto-balanced detection in the FTS. The system allows recording high-temperature water absorption spectra with a resolution of 1 GHz and a bandwidth of 50 nm in an acquisition time of 0.4 s, with absorption sensitivity of 4.2 × 10(-9) cm(-1) Hz(-1/2) per spectral element.

A thorough analysis of the shape and strength of Doppler-broadened wavelength modulated noise-immune cavity-enhanced optical heterodyne molecular spectroscopy signals is presented and their depende ...

The influence of optical saturation on noise-immune cavity-enhanced optical heterodyne molecular spectrometry (NICE-OHMS) signals from purely Doppler-broadened transitions is investigated experimen ...

Fiber-laser-based noise-immune cavity-enhanced optical heterodyne molecular spectrometry for Doppler-broadened detection of C2H2 in the parts per trillion range

The performance of fiber-laser-based noise-immune cavity-enhanced optical heterodyne molecular spectrometry (NICE-OHMS) has been improved by elimination of the technical constraints that limited its first demonstration. Doppler-broadened detection of C(2)H(2) and CO(2) at ~1531 nm is demonstrated using a cavity with a finesse of 4800. Frequency and wavelength modulated detection at absorption and dispersion phase are compared and the optimum mode of detection is discussed. A minimum detectable absorption of 8 x 10-(11) cm(-1), which corresponds to a detection limit of 4.5 ppt (2 ppt.m) for C(2)H(2), was obtained for an acquisition time of 0.7 s by lineshape fitting. The linearity of the pressure dependence of the signal strengths is investigated for both C(2)H(2) and CO(2).