On-line monitoring of biogenic isoprene emissions using photoacoustic spectroscopy

Isoprene (C₅H₈) is one of the most important biogenic volatile organic compounds (VOCs) in the atmosphere. To calculate the impact of isoprene on atmospheric processes models have been developed that describe the isoprene release from plants. Measurements of this release require techniques for a fast, sensitive, on-line isoprene detection. Photoacoustic (PA) spectroscopy is applied here for the first time to monitor biogenic isoprene emissions. A CO overtone PA spectrometer is used for the detection, probing the C-H stretching vibrations in the 3 to 4 μm range. This allows us to detect isoprene down to a few ppb with a time resolution of one minute in a continuous gas flow. The number of laser lines can be adjusted to meet the requirements of the respective experiment in terms of time resolution and selectivity against other possibly interfering VOCs. This results in a highly versatile instrument for the isoprene detection in biological experiments. Furthermore, the infrared fingerprint offers the potential to detect different isoprene isotopomers simultaneously, thus allowing us to carry out on-line labelling experiments. The new apparatus was used to study the light dependence of isoprene emission from Eucalyptus globulus. The results demonstrate, that the detector system is a promising tool for the study of plant gas emissions. It allows the validation of existing emission models which are important for atmospheric processes. Received: 18 March 1999 / Revised version: 23 August 1999 / Published online: 30 November 1999     

Soft X-ray amplification by Li-like Al10+ and Si11+ ions in recombining plasmas

Experimental studies of soft X-ray lasers were carried out on the six-beam laser facility and the LF 12 laser facility of SIOM. Using a home-made one-dimensional spatially resolved grazing incidence grating spectrograph, XUV amplification has been observed in Li-like aluminum and silicon ions, by irradiation of slab targets with a line-focused laser. Based on time-integrated measurement, gain coefficients are 3.1 cm^–1 for the 105.7 Å 5f–3d transition in Li-like Al ions, and 1.5 cm^–1 and 1.4 cm^–1 for the 88.9 Å 5f–3d and the 87.3 Å 5d–3p transitions in Li-like Si ions, respectively. The maximum gain × length products (GL) are about 2.5.     

Detection of atomic oxygen by laser-induced fluorescence spectroscopy at 130 nm

VUV radiation generated by stimulated Raman scattering from H₂ and tunable around 130 nm is applied to the detection of atomic oxygen produced in a flow-tube. Concentrations in the range to the detection of atomic oxygen produced in a flow-tube. Concentrations in the range of 10¹⁰ to 10¹¹ O-atoms per cm³ lead to fluorescence signals that can easily be detected on a nanosecond timescale. We deduce that oxygen impurities generated by plasma-wall interaction in present-day tokamak experiments should be measurable with spatial and temporal resolution applying this vuv source.     

Nonlinear absorption spectroscopy of the ethane molecule

By means of nonlinear absorption spectroscopy data necessary for the interpretation of molecular spectra can be obtained in such spectral regions, where conventional spectroscopic methods yield only a quasi-continuous absorption curve. Using a Zeeman-tuned He−Ne laser at the wavelength of 3.39μm we have measured significant differences in the intensity and temperature behaviour for several ethane absorption lines, the analysis of which made possible a preliminary qualitative assignment of these lines.     

Laser intracavity absorption spectroscopy

Emission spectra of multimode lasers are very sensitive to spectrally selective extinction in their cavity. This phenomenon allows the quantitative measurement of absorption. The sensitivity of measurements of intracavity absorption grows with the laser pulse duration. The ultimate sensitivity obtained with a cw laser is set by various perturbations of the light coherence, such as quantum noise, Rayleigh scattering, four-wave mixing by population pulsations, and stimulated Brillouin scattering. It depends on the particular laser type used, and on its operative parameters, for example pump power, cavity loss, cavity length, and length of the gain medium. Nonlinear mode-coupling dominates the dynamics of lasers that feature a thin gain medium, such as dye lasers, whereas Rayleigh scattering is more important in lasers with a long gain medium, such as doped fibre lasers, or the Ti:sapphire laser. The highest sensitivity so far has been obtained with a cw dye laser. It corresponds to 70000 km effective length of the absorption path. The ultimate spectral resolution is determined by the spectral width of mode emission, which is 0.7 Hz in this dye laser. High sensitivity and high temporal and spectral resolution allow various practical applications of laser intracavity spectroscopy, such as measurements and simulations of atmospheric absorption, molecular and atomic spectroscopy, process control, isotope separation, study of free radicals and chemical reactions, combustion diagnostics, spectroscopy of excited states and nonlinear processes, measurements of gain and of spectrally narrow light emission. Intracavity absorption in single-mode lasers shows enhanced sensitivity as well, although not as high as in multimode lasers. Received: 10 May 1999 / Published online: 29 July 1999     

Detection of argon and krypton traces in noble gases by diode laser absorption spectrometry

Wavelength modulation, diode laser atomic absorption spectrometry is applied to measure traces of argon and krypton in other noble gases. Strong transitions from long-lived metastable levels highly populated in a low-pressure dc discharge are induced with a standard diode laser in the spectral range around 811 nm. The detection limits achieved are in the lower ppbv range, and the residual concentrations of Kr and Ar traces in the utilized high-purity noble gases are measured. Received: 2 October 2000 / Final version: 3 May 2001 / Published online: 7 June 2001     

Near shot noise detection of oxygen in the A-band with vertical-cavity surface-emitting lasers

A dual-beam laser absorption spectrometer with balanced detection for high sensitivity detection of oxygen via the A-band at 760 nm is described. The 2×2 vertical-cavity surface-emitting laser arrays used for this set-up are characterized by their wavelength tuning behavior with temperature and current, amplitude modulation, side-mode suppression ratio and polarization contrast. The spectrometer performance is determined over time periods of up to 10 h using the variation in the differential absorption between two beam paths. With the R11R11 line at STP, 670 μW laser power and 200 mm-long absorption cells, we realized an excellent linearity (R=0.9999) and over a 5-min interval a record sensitivity for VCSEL-based spectrometers of 35 ppmV, corresponding to an optical density (O.D.) of 7×10^-7. For this specific set-up, this sensitivity is only a factor of 2.7 above the shot noise limit, giving us a normalized detection limit of 7.6 ppmV·m·. Over a 10-h interval we achieved a standard deviation of 65 ppmV. Received: 26 July 2000 / Revised version: 1 November 2000 / Published online: 6 December 2000     

Analysis of plume-buffer gas interaction through molecular and atomic oxygen absorption spectroscopy

We present results acquired by using in-situ diagnostics based on atomic and molecular oxygen absorption spectroscopy during laser ablation in the presence of an O₂ environment. Our investigation provides detailed space- and time-resolved information on the relative density of atomic and molecular oxygen in the plume, and demonstrates a strong correlation between their behavior. The results shed light on the occurrence of reactive-collisional processes involving the ablated material and the environment, leading to O₂ dissociation.     

Lineshape effects in atomic absorption spectroscopy

Deviations from Beer's Law caused by the relative lineshape functions of source and absorber in atomic absorption experiments are considered. The validity of using a modified form of the law incorporating a correction factor γ, which is particularly convenient in time-resolved atomic absorption experiments, to account for these deviations, has been critically examined for a wide range of source and absorber lineshapes using numerical evaluation of the transmission integrals involved. It is concluded that there is, in general, no theoretical justification for the use of such a γ factor, except in the case of large source linewidth/absorber linewidth ratios when the line broadening in the absorber involves a significant homogeneous (Lorentzian) contribution. The use of empirically determined γ factors, much different from unity to analyse experimental data, should be viewed with suspicion unless direct evidence is presented to show that under the experimental conditions γ happens to be constant or slowly varying.     

Intracavity laser absorption spectroscopy and cavity ring-down spectroscopy in low-pressure flames

Intracavity laser absorption spectroscopy (ICLAS) and cavity ring-down spectroscopy (CRDS) have been used for measurement of the NH₂-radical spectrum near 643 nm. NH₂ was obtained in low-pressure methane/air flat flames doped with minor amounts of ammonia (as low as 0.023%). The NH₂ concentration was measured both by CRDS and ICLAS in the same conditions. This enables us to compare the practical sensitivity of the two methods. Both methods were also used for measurements in a sooting acetylene/air flame (ϕ = 2.6). The comparative advantages of the methods and their complementarities are discussed.     

In situ soft X-ray absorption spectroscopy of flames

The feasibility of in situ soft X-ray absorption spectroscopy for imaging carbonaceous species in hydrocarbon flames is demonstrated using synchrotron radiation. Soft X-rays are absorbed by core level electrons in all carbon atoms regardless of their molecular structure. Core electron spectroscopy affords distinct advantages over valence spectroscopy, which forms the basis of traditional laser diagnostic techniques for combustion. In core level spectroscopy, the transition linewidths are predominantly determined by the instrument response function and the decay time of the core–hole, which is on the order of a femtosecond. As a result, soft X-ray absorption measurements can be performed in flames with negligible Doppler and collisional broadening. Core level spectroscopy has the further advantage of measuring all carbonaceous species regardless of molecular structure in the far-edge region, whereas near-edge features are molecule specific. Interferences from non-carbon flame species are unstructured and can be subtracted. In the present study, absorption measurements in the carbon K-edge region are demonstrated in low-pressure (P _total = 20–30 Torr) methane jet flames. Two-dimensional imaging of the major carbonaceous species, CH₄, CO₂, and CO, is accomplished by tuning the synchrotron radiation to the respective carbon K-edge, near-edge X-ray absorption fine structure (NEXAFS) transitions and scanning the burner.     

Fast, low-noise, mode-by-mode, cavity-enhanced absorption spectroscopy by diode-laser self-locking

A new technique of cavity enhanced absorption spectroscopy is described. Molecular absorption spectra are obtained by recording the transmission maxima of the successive TEM_oo resonances of a high-finesse optical cavity when a Distributed Feedback Diode Laser is tuned across them. A noisy cavity output is usually observed in such a measurement since the resonances are spectrally narrower than the laser. We show that a folded (V-shaped) cavity can be used to obtain selective optical feedback from the intracavity field which builds up at resonance. This induces laser linewidth reduction and frequency locking. The linewidth narrowing eliminates the noisy cavity output, and allows measuring the maximum mode transmissions accurately. The frequency locking permits the laser to scan stepwise through the successive cavity modes. Frequency tuning is thus tightly optimized for cavity mode injection. Our setup for this technique of Optical-Feedback Cavity-Enhanced Absorption Spectroscopy (OF-CEAS) includes a 50 cm folded cavity with finesse ∼20 000 (ringdown time ∼20 μs) and allows recording spectra of up to 200 cavity modes (2 cm⁻¹) using 100 ms laser scans. We obtain a noise equivalent absorption coefficient of ∼5×10⁻¹⁰ cm⁻¹ for 1 s averaging over scans, with a dynamic range of four orders of magnitude.     

Detection of weak useful signals on the background of noise in atomic absorption spectroscopy

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 56, No. 3, pp. 467–473, March, 1992.     

Photoacoustic analysis of stimulated emission in pulsed dye lasers

Stimulated emission in pulsed dye lasers was characterized in several experimental conditions by analyzing the changes in the acoustic signals generated in a dye solution, with the dye laser cavity either active or inhibited (i.e., by blocking the optical path or misaligning of the optical components). Pump energy threshold, optimum dye concentration, tuning range and maximum-emission wavelength of a rhodamine 6G dye laser were measured by this method. An approximate model for the photoacoustic signal generation consistent with the experiments is presented.Member of CONICET     

Studies of recombination X-ray-laser gain and gain-medium uniformity

The time evolution of the uniformity of the line-shaped X-ray-laser gain medium and the spatial characteristics of the recombination X-ray-laser gains of the Li-like ions are studied using long (900 ps) and short (100 ps) laser pulses.     

The escape factor in atomic absorption spectroscopy

Values of the escape factor have beeb calculated from atomic absorption measurements for a wide range of concentrations of Li, K, Cu, and Ag at the resonance lines 6707.84, 7664.01, 3427.54 and 3382.89 A, respectively. Different approximations were investigated and the optical depths limits for which each approximation is reliable have been predicted. The dependence of the escape factor on the total number of atomos in the ground state is discussed. Atomic absorption phenomena are explained in terms of the escape factor, especially at high concentrations.     

Characterization of a Co-Se thin film by scanning Auger microscopy and Raman spectroscopy

Scanning Auger microscopy and micro-Raman spectroscopy are combined to characterize a Co-Se thin film sample, containing 84 at.% Se, which had been modified in localized areas following excitation with an intense focused Ar⁺ laser (514.5 nm). The information obtained helps to establish that a previous assignment for a Co-Se sample of Raman features between 168 and 175 cm⁻¹ actually refers to an oxygenated Co-Se species, and that Co-Se interactions in a Se-rich environment give rise to Raman structure between 181 and 184 cm⁻¹. Comparisons are made for the use of Ar⁺ and HeNe laser sources for Raman measurements in this context; the latter in general gives both better resolution and better signal-to-noise characteristics.     

CO-laser-based photoacoustic trace-gas detection: applications in postharvest physiology

2 measurements using polarographic oxygen sensors. Received: 13 March 1998/Revised version: 13 May 1998