Ammonia detection by using quantum-cascade laser photoacoustic spectroscopy

A pulsed quantum-cascade distributed-feedback laser, temperature tunable from -41 degrees C to +31.6 degrees C, and a resonant differential photoacoustic detector are used to measure trace-gas concentrations to as low as 66 parts per 10(9) by volume (ppbv) ammonia at a low laser power of 2 mW. Good agreement between the experimental spectrum and the simulated HITRAN spectrum of NH3 is found in the spectral range between 1046 and 1052 cm(-1). A detection limit of 30 ppbv ammonia at a signal-to-noise ratio of 1 was obtained with the quantum-cascade laser (QCL) photoacoustic (PA) setup. Concentration changes of approximately 50 ppbv were detectable with this compact and versatile QCL-based PA detection system. The performance of the PA detector, characterized by the product of the incident laser power and the minimum detectable absorption coefficient, was 4.7 x 10-9 W cm(-1).     

Gas detection by correlation spectroscopy employing a multimode diode laser

A gas sensor based on the gas-correlation technique has been developed using a multimode diode laser (MDL) in a dual-beam detection scheme. Measurement of CO(2) mixed with CO as an interfering gas is successfully demonstrated using a 1570 nm tunable MDL. Despite overlapping absorption spectra and occasional mode hops, the interfering signals can be effectively excluded by a statistical procedure including correlation analysis and outlier identification. The gas concentration is retrieved from several pair-correlated signals by a linear-regression scheme, yielding a reliable and accurate measurement. This demonstrates the utility of the unsophisticated MDLs as novel light sources for gas detection applications.     

Fiber-amplifier-enhanced photoacoustic spectroscopy with near-infrared tunable diode lasers

A new approach to wavelength-modulation photoacoustic spectroscopy is reported, which incorporates diode lasers in the near infrared and optical fiber amplifiers to enhance sensitivity. We demonstrate the technique with ammonia detection, yielding a sensitivity limit less than 6 parts in 10(9), by interrogating a transition near 1532 nm with 500 mW of output power from the fiber amplifier, an optical pathlength of 18.4 cm, and an integration time constant of 10 s. This sensitivity is 15 times better than in prior published results for detecting ammonia with near-infrared diode lasers. The normalized minimum detectable fractional optical density, alphaminl, is 1.8 x 10(-8); the minimum detectable absorption coefficient, alphamin, is 9.5 x 10(-10) cm(-1); and the minimum detectable absorption coefficient normalized by power and bandwidth is 1.5 x 10(-9) W cm(-1)/square root Hz. These measurements represent what we believe to be the first use of fiber amplifiers to enhance photoacoustic spectroscopy, and this technique is applicable to all other species that fall within the gain curves of optical fiber amplifiers.     

Optically multiplexed multi-gas detection using quantum cascade laser photoacoustic spectroscopy

We report high-throughput, nondispersive optical multiplexing of laser beams using a scanning galvanometer. We have utilized this technique for multispecies trace-gas detection using multiple quantum cascade laser photoacoustic spectroscopy. We demonstrate switching from one laser to another in less than 1 s, a performance level needed for a comprehensive multispecies sensor, and a high signal-to-noise ratio detection of five gaseous components, NH(3), NO(2), dimethyl methyl phosphonate (DMMP, a simulant for nerve agents), acetone, and ethylene glycol, in a room air gas mixture containing approximately 3 ppb of NH(3), approximately 8 ppb of NO(2), approximately 20 ppb of DMMP, approximately 30 ppb of acetone, and approximately 40 ppb of ethylene glycol.     

Piezo-locking a diode laser with saturated absorption spectroscopy

We demonstrate modulation-based frequency locking of an external cavity diode laser, utilizing a piezo-electrically actuated mirror, external to the laser cavity, to create an error signal from saturated absorption spectroscopy. With this method, a laser stabilized to a rubidium hyperfine transition has a FWHM of 130 kHz over seconds, making the locked laser suitable for experiments in atomic physics, such as creating and manipulating Bose-Einstein condensates. This technique combines the advantages of low-amplitude modulation, simplicity, performance, and price, factors that are usually considered to be mutually exclusive.     

Sub-parts-per-billion level detection of dimethyl methyl phosphonate (DMMP) by quantum cascade laser photoacoustic spectroscopy

The need for the detection of chemical warfare agents (CWAs) is no longer confined to battlefield environments because of at least one confirmed terrorist attack, the Tokyo Subway [Emerg. Infect. Dis. 5, 513 (1999)] in 1995, and a suspected, i.e., a false-alarm of a CWA in the Russell Senate Office Building [Washington Post, 9 February 2006, p. B01]. Therefore, detection of CWAs with high sensitivity and low false-alarm rates is considered an important priority for ensuring public safety. We report a minimum detection level for a CWA simulant, dimethyl methyl phosphonate (DMMP), of <0.5 ppb (parts in 10(9)) by use of a widely tunable external grating cavity quantum cascade laser and photoacoustic spectroscopy. With interferents present in Santa Monica, California street air, we demonstrate a false-alarm rate of 1:10(6) at a detection threshold of 1.6 ppb.     

Stable isotopic analysis of atmospheric methane by infrared spectroscopy by use of diode laser difference-frequency generation

An infrared absorption spectrometer has been constructed to measure the stable isotopic composition of atmospheric methane samples. The spectrometer employs periodically poled lithium niobate to generate 15 microW of tunable difference-frequency radiation from two near-infrared diode lasers that probe the nu3 rotational-vibrational band of methane at 3.4 microm. To enhance the signal, methane is extracted from 25 l of air by use of a cryogenic chromatographic column and is expanded into the multipass cell for analysis. A measurement precision of 12 per thousand is demonstrated for both delta13C and deltaD.     

Near-infrared diode laser based spectroscopic detection of ammonia: a comparative study of photoacoustic and direct optical absorption methods

A photoacoustic spectroscopic (PAS) and a direct optical absorption spectroscopic (OAS) gas sensor, both using continuous-wave room-temperature diode lasers operating at 1531.8 nm, were compared on the basis of ammonia detection. Excellent linear correlation between the detector signals of the two systems was found. Although the physical properties and the mode of operation of both sensors were significantly different, their performances were found to be remarkably similar, with a sub-ppm level minimum detectable concentration of ammonia and a fast response time in the range of a few minutes.     

Wavelength-modulation detection of acetylene with a near-infrared external-cavity diode laser

An external-cavity diode laser operating at 1500 nm was used to record the combination band of acetylene (C(2)H(2)). By combination of wavelength-modulation spectroscopy with a noise-canceler detection circuit, a minimum detectable absorbance of 4.8 × 10(-4) with a 300-ms time constant was achieved, although this result was limited by étalon fringes. When combined with this detection technique, continuous, widely tunable output from an external-cavity laser is ideally suited for high-resolution absorption spectroscopy with excellent sensitivity.     

Sensitive absorption spectroscopy by use of an asymmetric multiple-quantum-well diode laser in an external cavity

We have developed a broadly tunable diode laser system by employing custom-designed asymmetric multiple-quantum-well (AMQW) InGaAsP lasers in an external cavity configuration. Feedback is provided by a diffractive optical element with high coupling efficiency and wavelength selectivity, allowing for single-mode tuning of the output wavelength by varying the external cavity length. This tunable laser system was used experimentally to perform absorption spectroscopy on weak CO(2) lines over a broad wavelength region in the near infrared. An experimental tuning range of 80 nm has been observed for a laser cavity length of 600 mum, which is double the tuning range found with conventional, uncoated quantum-well lasers. We achieved a detection sensitivity of 5 x 10(-6) at 95% confidence over the wavelength range of 1.54-1.62 mum by employing a second-harmonic detection technique. The theoretical predictions of a broad gain profile from an ambipolar rate equation model are found to correspond to the experimentally observed increased tunability of the uncoated AMQW lasers.     

Low-frequency wavelength modulation spectroscopy with D2 transition of atomic cesium by use of an external-cavity diode laser

Low-frequency wavelength modulation spectroscopy is acquired with an external-cavity diode laser. The wavelength modulation is achieved with voltage tuning by means of scanning with the piezoelectric stepper motor, which rotates the end mirror in the laser cavity. With optimum 1-kHz frequency modulation and harmonic detection, direct absorption experiments for the 6S(1/2)(F = 4) --> 6P(3/2) transition of the cesium D(2) line were carried out. We found that 6f-harmonic detection is best here with a signal-to-noise voltage ratio of 460.     

Development of photoacoustic spectroscopy with a piezofilm

We have developed photoacoustic spectroscopy with a piezofilm. A piezofilm is a piezoelectric element made from plastic polyvinylidene fluoride having piezoelectrical effect. Photoacoustic spectra (375-675 nm) of water, dye aqueous solution, and benzene, are measured with a xenon lamp. The piezofilm is directly immersed in the liquid samples for sensitive detection of the signal. The sensitivity of the method is shown to be as high as for photothermal deflection spectroscopy. Compared with the conventional methods such as photoacoustic spectroscopy with a piezoceramic and photothermal spectroscopy with a double beam configuration, the present method is favorable from its handy and simpler experimental setup.     

Assessing soil respiration by means of near-infrared diode laser spectroscopy

High-resolution diode laser spectroscopy in the near-infrared region is applied to the accurate measurement of soil respiration. In particular, the use of a diode-laser-based spectrometer has allowed the implementation, for the first time, of a static accumulation method capable of measuring soil respiration from continuous measurements of CO(2) concentrations, with minor perturbation on soil respiration as well as on CO(2) transport and emission. The system has been tested in a laboratory experiment by detection of CO(2) production from sandy matrices, inoculated with active soil microbes and supplied with different amounts of decomposable plant material. Respiration rates of all samples were then retrieved using a diffusion model. The results of the laboratory tests are in agreement with those expected on the basis of sample composition. Examples of operation with real soil samples are also reported. We discuss the possible field application of the system, in conjunction with closed static soil chambers.     

High-resolution absorption measurements by use of two-tone frequency-modulation spectroscopy with diode lasers

The capability of two-tone frequency-modulation spectroscopy (TTFMS) in deriving spectral line-shape information was investigated. Two oxygen A-band transitions at 760 nm were selected, and the Voigt profile and two different collisionally narrowed line profiles were employed in their analysis. By means of a least-squares fitting procedure, we obtained accurate information regarding transition strengths and pressure-induced broadening, shift, and narrowing coefficients. Both TTFMS and direct absorption line shapes were modeled with deviations as small as 0.3% over a wide pressure range by use of the collisionally narrowed line profiles. Line parameters measured with TTFMS showed excellent agreement with the parameters measured with direct absorption. The experimental technique used constant-current fast-wavelength scanning, which improved measurement accuracy.     

Methodology for detection of carbon monoxide in hot, humid media by telecommunication distributed feedback laser-based tunable diode laser absorption spectrometry

Detection of carbon monoxide (CO) in combustion gases by tunable diode laser spectrometry is often hampered by spectral interferences from H2O and CO2. A methodology for assessment of CO in hot, humid media using telecommunication distributed feedback lasers is presented. By addressing the R14 line at 6395.4 cm(-1), and by using a dual-species-fitting technique that incorporates the fitting of both a previously measured water background reference spectrum and a 2f-wavelength modulation lineshape function, percent-level concentrations of CO can be detected in media with tens of percent of water (c(H2O)≤40%) at T≤1000?°C with an accuracy of a few percent by the use of a single reference water spectrum for background correction.     

Analysis of isotopic CO(2) mixtures by laser photoacoustic spectroscopy

Photoacoustic spectroscopic studies on a mixture of six CO(2) isotopes ((12) C(16) O(2), (12) C(18) O(2), (13) C (16) O(2), (13) C(18) O(2), (16) O(12) C(18) O, and (16) O(13) C(18) O) in the wavelength range of 9-11 mum by use of a home-built high-pressure continuously tunable CO(2) laser with a bandwidth of 0.017 cm(-1) are discussed. The concentrations of all CO(2) isotopes present in the mixture could be determined with good accuracy. Furthermore, the previously unknown absorption cross sections of some important lines of the(12) C(18) O(2), (13) C(18) O(2), and (16)O (13) C(18) O isotopes in the 9-11-mum range are reported.     

Multipass Michelson interferometer with the use of a wavelength-modulated laser diode

An improved multipass Michelson interferometer is implemented. This technique uses the fact that the wavelength of a laser diode varies in proportion to the diode's injection current. With this method the sensitivity augmentation is accomplished by inserting a beam splitter into one arm of the interferometer, resulting in multiple reflections between the end mirror and the beam splitter. In addition, the interference of laser beams reflected from two arms can be accomplished with unequal arms in the condition of a short coherence length. The sensitivity increase of interference fringes and the compensation of the short coherence length have been demonstrated in experiments.     

External photoacoustic detection of a trace vapor inside a multimode laser.

We combine highly sensitive intracavity absorption spectroscopy in a multimode laser with external photoacoustic detection, providing high detectivity. Photoacoustic measurements of the intracavity iodine concentration in a Rhodamine 6G laser are compared with simultaneous spectral recordings. They demonstrate slightly improved overall sensitivity and a greatly enhanced dynamic range of 5 orders of magnitude that may be shifted along the absolute scale of absorber density.     

External cavity diode laser based photoacoustic detection of CO2 at 1.43 microm: the effect of molecular relaxation

Photoacoustic spectroscopy, based on an external cavity diode laser operating at 1431 nm, was used for measuring CO2 concentration as a minority component in a gas mixture. By using N2 as a buffer gas, a molecular relaxation effect was observed, which influenced both the amplitude and the phase of the measured photoacoustic signal and consequently reduced the sensitivity of the PA system. This molecular relaxation effect could be suppressed by adding water vapor of a constant and relatively high (approximately 4%) concentration to the gas sample. In parallel with this, the arising spectral interference between H2O and CO2 necessitated the development of a simple yet efficient signal analysis method, which increased the sensitivity of the system by more than one order of magnitude and accordingly reduced the minimum detectable CO2 concentration down to approximately 1000 ppm.