Modulation cancellation method for isotope 18O/16O ratio measurements in water.

The application of an innovative spectroscopic balancing technique to measure the isotope 18O/16O ratio in water vapor is reported. Quartz enhanced photoacoustic spectroscopy has been employed as the absorption sensing technique. Two isotope absorption lines with the same quantum numbers, with very close lower energy levels, have been selected to limit the sensitivity to temperature variations and guarantee identical broadening as well as relaxation properties. The sensitivity in measuring the deviation from a standard sample δ18O is 1.4‰, in 200 sec of integration time.

Modulation cancellation method for measurements of small temperature differences in a gas.

An innovative spectroscopic technique based on balancing and cancellation of modulated signals induced by two excitation sources is reported. For its practical implementation, we used quartz-enhanced photoacoustic spectroscopy as an absorption-sensing technique and applied the new approach to measure small temperature differences between two gas samples. The achieved sensitivity was 30 mK in 17 s. A theoretical sensitivity analysis is presented, and the applicability of this method to isotopic measurements is discussed.

Trace gas detection based on off-beam quartz enhanced photoacoustic spectroscopy: optimization and performance evaluation.

A gas sensor based on off-beam quartz enhanced photoacoustic spectroscopy was developed and optimized. Specifically, the length and diameter of the microresonator tube were optimized, and the outer tube shape is modified for enhancing the trace gas detection sensitivity. The impact of the distance between the quartz tuning fork and an acoustic microresonator on the sensor performance was experimentally investigated. The sensor performance was evaluated by determining the detection sensitivity to H(2)O vapor in ambient air at normal atmospheric pressure. A normalized noise equivalent absorption coefficient (1σ) of 6.2×10(-9) cm(-1) W/Hz(1/2) was achieved.

Resonant optothermoacoustic detection: technique for measuring weak optical absorption by gases and micro-objects.

We report a laser spectroscopy technique for detecting optical absorption in gases and micro-objects via linked thermal effects and by using a sharp mechanical resonance in a quartz crystal. The performance of this technique is studied using near-IR diode lasers and two gases, pure CO(2) and C(2)H(2) diluted in nitrogen. A 7.3 × 10(-8) cm(-1)W/(Hz)(1/2) noise equivalent sensitivity to absorption in gases is demonstrated. Based on experimental results, it was estimated that 10(-8) fractional absorption of optical radiation by a micro-object deposited on a thin transparent fiber can be detected.

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

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.

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.

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.

Monitoring of ethylene by a pulsed quantum cascade laser.

We report on the development and performance of a gas sensor based on a quantum cascade laser operating at a wavelength of approximately 10 microns to measure ethylene (C2H4) concentrations by use of a rotational component of the fundamental nu 7 band. The laser is thermoelectrically cooled and operates in a pulsed mode. The influence of pulse-to-pulse fluctuations is minimized by use of a reference beam and a single detector with time discriminating electronics. Gas absorption is recorded in a 100-m optical path-length astigmatic Herriott cell. With a 10-kHz pulse repetition rate and an 80-s total acquisition time, a noise equivalent sensitivity of 30 parts per billion has been demonstrated. The sensor has been applied to monitor C2H4 in vehicle exhaust as well as in air collected in a high-traffic urban tunnel.

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.

Carbonyl sulfide detection with a thermoelectrically cooled midinfrared quantum cascade laser.

A compact absorption spectrometer with a midinfrared tunable quantum cascade laser operating at 4.86 microm (2054 cm(-1)) is used to measure lower concentrations of carbonyl sulfide (COS) in air. A detection sensitivity of approximately 30 parts in 10(9) of COS and the selectivity of two stable isotopes, 12C(16)O32S and 12C(16)O34S, are demonstrated. Specifically, the feasibility of detecting COS in expired human breath as a potential noninvasive medical diagnostic tool is investigated.

Transportable automated ammonia sensor based on a pulsed thermoelectrically cooled quantum-cascade distributed feedback laser.

A compact ammonia sensor based on a 10-microm single-frequency, thermoelectrically cooled, pulsed quantum-cascade laser with an embedded distributed feedback structure has been developed. To measure NH3 concentrations, we scanned the laser over two absorption lines of its fundamental v2 band. A sensitivity of better than 0.3 parts per million was achieved with just a 1-m optical path length. The sensor is computer controlled and automated to monitor NH3 concentrations continuously for extended periods of time and to store data in the computer memory.

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).