Anatoliy A. Kosterev

Applications of quartz tuning forks in spectroscopic gas sensing

A recently introduced approach to photoacoustic detection of trace gases utilizing a quartz tuning fork (TF) as a resonant acoustic transducer is described in detail. Advantages of the technique called quartz-enhanced photoacoustic spectroscopy (QEPAS) compared to conventional resonant photoacoustic spectroscopy include QEPAS sensor immunity to environmental acoustic noise, a simple absorption detection module design, and its capability to analyze gas samples ∼1mm3 in volume. Noise sources and the TF properties as a function of the sampled gas pressure, temperature and chemical composition are analyzed. Previously published results for QEPAS based chemical gas sensing are summarized. The achieved sensitivity of 5.4×10−9cm−1W∕√Hz is compared to recent published results of photoacoustic gas sensing by other research groups. An experimental study of the long-term stability of a QEPAS-based ammonia sensor is presented. The results of this study indicate that the sensor exhibits very low drift, which allows da...

Mid-infrared quantum cascade laser based off-axis integrated cavity output spectroscopy for biogenic nitric oxide detection

Tunable-laser absorption spectroscopy in the mid-IR spectral region is a sensitive analytical technique for trace-gas quantification. The detection of nitric oxide (NO) in exhaled breath is of particular interest in the diagnosis of lower-airway inflammation associated with a number of lung diseases and illnesses. A gas analyzer based on a continuous-wave mid-IR quantum cascade laser operating at approximately 5.2 microm and on off-axis integrated cavity output spectroscopy (ICOS) has been developed to measure NO concentrations in human breath. A compact sample cell, 5.3 cm in length and with a volume of < 80 cm3, that is suitable for on-line and off-line measurements during a single breath cycle, has been designed and tested. A noise-equivalent (signal-to-noise ratio of 1) sensitivity of 10 parts in 10(9) by volume (ppbv) of NO was achieved. The combination of ICOS with wavelength modulation resulted in a 2-ppbv noise-equivalent sensitivity. The total data acquisition and averaging time was 15 s in both cases. The feasibility of detecting NO in expired human breath as a potential noninvasive medical diagnostic tool is discussed.

Cavity ringdown spectroscopic detection of nitric oxide with a continuous-wave quantum-cascade laser

A spectroscopic gas sensor for nitric oxide (NO) detection based on a cavity ringdown technique was designed and evaluated. A cw quantum-cascade distributed-feedback laser operating at 5.2 mum was used as a tunable single-frequency light source. Both laser-frequency tuning and abrupt interruptions of the laser radiation were performed through manipulation of the laser current. A single ringdown event sensitivity to absorption of 2.2 x 10(-8) cm(-1) was achieved. Measurements of parts per billion (ppb) NO concentrations in N(2) with a 0.7-ppb standard error for a data collection time of 8 s have been performed. Future improvements are discussed that would allow quantification of NO in human breath.

Methane concentration and isotopic composition measurements with a mid-infrared quantum-cascade laser

A quantum-cascade laser operating at a wavelength of 8.1 micrometers was used for high-sensitivity absorption spectroscopy of methane (CH4). The laser frequency was continuously scanned with current over more than 3 cm-1, and absorption spectra of the CH4 nu 4 P branch were recorded. The measured laser linewidth was 50 MHz. A CH4 concentration of 15.6 parts in 10(6) ( ppm) in 50 Torr of air was measured in a 43-cm path length with +/- 0.5-ppm accuracy when the signal was averaged over 400 scans. The minimum detectable absorption in such direct absorption measurements is estimated to be 1.1 x 10(-4). The content of 13CH4 and CH3D species in a CH4 sample was determined.

Ammonia detection by use of quartz-enhanced photoacoustic spectroscopy with a near-IR telecommunication diode laser

A gas sensor based on quartz-enhanced photoacoustic detection and a fiber-coupled telecommunication distributed-feedback diode laser was designed and characterized for trace NH3 monitoring at a 1.53-microm wavelength (overtone absorption region). Signal and noise dependence on gas pressure were studied to optimize sensor performance. The ammonia concentration resulting in a noise-equivalent signal was found to be 0.65 parts per million by volume with 38-mW optical excitation power and a lock-in amplifier time constant of 1 s. This corresponds to a normalized absorption sensitivity of 7.2 x 10(-9) cm(-1) W/Hz1/2, comparable with detection sensitivity achieved in conventional photoacoustic spectroscopy. The sensor architecture can be the basis for a portable gas analyzer.

QEPAS based detection of broadband absorbing molecules using a widely tunable, cw quantum cascade laser at 8.4 μm.

Detection of molecules with wide unresolved rotationa-lvibrational absorption bands is demonstrated by using Quartz Enhanced Photoacoustic Spectroscopy and an amplitude modulated, high power, thermoelectrically cooled quantum cascade laser operating at 8.4 mum in an external cavity configuration. The laser source exhibits single frequency tuning of 135 cm-1 with a maximum optical output power of 50 mW. For trace-gas detection of Freon 125 (pentafluoroethane) at 1208.62 cm-1 a normalized noise equivalent absorption coefficient of NNEA=2.64x10(-9) cm?(-1)W/Hz(1/2)was obtained. Noise equivalent sensitivity at ppbv level as well as spectroscopic chemical analysis of a mixture of two broadband absorbers (Freon 125 and acetone) with overlapping absorption spectra were demonstrated.

Trace-gas detection in ambient air with a thermoelectrically cooled, pulsed quantum-cascade distributed feedback laser

A pulsed quantum-cascade distributed feedback laser operating at near room temperature was used for sensitive high-resolution IR absorption spectroscopy of ambient air at a wavelength of approximately 8 microm. Near-transform-limited laser pulses were obtained owing to short (approximately 5-ns) current pulse excitation and optimized electrical coupling. Fast and slow computer-controlled frequency scanning techniques were implemented and characterized. Fast computer-controlled laser wavelength switching was used to acquire second-derivative absorption spectra. The minimum detectable absorption was found to be 3 x 10(-4) with 10(5) laser pulses (20-kHz repetition rate), and 1.7 x 10(-4) for 5 x 10(5) pulses, based on the standard deviation of the linear regression analysis.

Effective utilization of quantum-cascade distributed-feedback lasers in absorption spectroscopy

A variable duty cycle quasi-cw frequency scanning technique was applied to reduce thermal effects resulting from the high heat dissipation of type I quantum-cascade lasers. This technique was combined with a 100-m path-length multipass cell and a zero-air background-subtraction technique to enhance detection sensitivity to a parts-in-10(9) (ppb) concentration level for spectroscopic trace-gas detection of CH4, N2O, H2O, and C2H5OH in ambient air at 7.9 micrometers. A new technique for analysis of dense high resolution absorption spectra was applied to detection of ethanol in ambient air, yielding a 125-ppb detection limit.

Application of a widely electrically tunable diode laser to chemical gas sensing with quartz-enhanced photoacoustic spectroscopy

A near-infrared diode laser with sample-grating distributed Bragg reflectors was used as a widely tunable spectroscopic source for multispecies chemical sensing. Quartz-enhanced photoacoustic spectroscopy was utilized to obtain high absorption sensitivity in a compact gas cell. CO2, H2O C2H2, and NH3 were monitored. A noise equivalent sensitivity of 8 x 10(-9) cm(-1) W(-1) Hz(-1/2)for NH3 detection was achieved, which corresponds to a NH3 mixing ratio of 4.4 parts in 10(6) by volume (ppmv) with a 1-s time constant and available 5.2-mW optical power in the gas cell.

Thermoelectrically cooled quantum-cascade-laser-based sensor for the continuous monitoring of ambient atmospheric carbon monoxide

We report the first application of a thermoelectrically cooled, distributed-feedback quantum-cascade laser for continuous spectroscopic monitoring of CO in ambient air at a wavelength of 4.6 microm. A noise-equivalent detection limit of 12 parts per billion was demonstrated experimentally with a 102-cm optical pathlength and a 2.5-min data acquisition time at a 10-kHz pulsed-laser repetition rate. This sensitivity corresponds to a standard error in fractional absorbance of 3 x 10(-5).