Gerard Wysocki

Recent advances of laser-spectroscopy-based techniques for applications in breath analysis

Laser absorption spectroscopy (LAS) in the mid-infrared region offers a promising new effective technique for the quantitative analysis of trace gases in human breath. LAS enables sensitive, selective detection, quantification and monitoring in real time, of gases present in breath. This review summarizes some of the recent advances in LAS based on semiconductor lasers and optical detection techniques for clinically relevant exhaled gas analysis in breath, specifically such molecular biomarkers as nitric oxide, ammonia, carbon monoxide, ethane, carbonyl sulfide, formaldehyde and acetone.

Ultrasensitive detection of nitric oxide at 5.33 μm by using external cavity quantum cascade laser-based Faraday rotation spectroscopy

A transportable prototype Faraday rotation spectroscopic system based on a tunable external cavity quantum cascade laser has been developed for ultrasensitive detection of nitric oxide (NO). A broadly tunable laser source allows targeting the optimum Q3/2(3/2) molecular transition at 1875.81 cm−1 of the NO fundamental band. For an active optical path of 44 cm and 1-s lock-in time constant minimum NO detection limits (1σ) of 4.3 parts per billion by volume (ppbv) and 0.38 ppbv are obtained by using a thermoelectrically cooled mercury–cadmium–telluride photodetector and liquid nitrogen-cooled indium–antimonide photodetector, respectively. Laboratory performance evaluation and results of continuous, unattended monitoring of atmospheric NO concentration levels are reported.

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.

Molecular dispersion spectroscopy for chemical sensing using chirped mid-infrared quantum cascade laser

A spectroscopic method of molecular detection based on dispersion measurements using a frequency-chirped laser source is presented. An infrared quantum cascade laser emitting around 1912 cm(-1) is used as a tunable spectroscopic source to measure dispersion that occurs in the vicinity of molecular ro-vibrational transitions. The sample under study is a mixture of nitric oxide in dry nitrogen. Two experimental configurations based on a coherent detection scheme are investigated and discussed. The theoretical models, which describe the observed spectral signals, are developed and verified experimentally. The method is particularly relevant to optical sensing based on mid-infrared quantum cascade lasers as the high chirp rates available with those sources can significantly enhance the magnitude of the measured dispersion signals. The method relies on heterodyne beatnote frequency measurements and shows high immunity to variations in the optical power received by the photodetector.

Pulsed quantum-cascade laser-based sensor for trace-gas detection of carbonyl sulfide

Simultaneous exhaled carbonyl sulfide (OCS) and carbon dioxide concentration measurements in human breath are demonstrated with a compact pulsed quantum-cascade laser-based gas sensor. We achieved a noise-equivalent sensitivity (1sigma) of 1.2 parts per billion by measuring a well-isolated OCS P(11) absorption line in the v3 band at 2057.6 cm(-1) using an astigmatic Herriott cell of 36-m optical path length and 0.4-s acquisition time.

Performance of an exhaled nitric oxide and carbon dioxide sensor using quantum cascade laser-based integrated cavity output spectroscopy.

Exhaled nitric oxide (NO) is an important biomarker in asthma and other respiratory disorders. The optical performance of a NOCO(2) sensor employing integrated cavity output spectroscopy (ICOS) with a quantum cascade laser operating at 5.22 microm capable of real-time NO and CO(2) measurements in a single breath cycle is reported. A NO noise-equivalent concentration of 0.4 ppb within a 1-sec integration time is achieved. The off-axis ICOS sensor performance is compared to a chemiluminescent NO analyzer and a nondispersive infrared (NDIR) CO(2) absorption capnograph. Differences between the gas analyzers are assessed by the Bland-Altman method to estimate the expected variability between the gas sensors. The off-axis ICOS sensor measurements are in good agreement with the data acquired with the two commercial gas analyzers. This work demonstrates the performance characteristics and merits of mid-infrared spectroscopy for exhaled breath analysis.

Dual interband cascade laser based trace-gas sensor for environmental monitoring

The development of an interband cascade laser (ICL) based spectroscopic trace-gas sensor for the simultaneous detection of two atmospheric trace gases is reported. The sensor performance was evaluated using two ICLs capable of targeting formaldehyde (H2CO) and ethane (C2H6). Minimum detection limits of 3.5 ppbV for H2CO and 150 pptV for C2H6 was demonstrated with a 1 s integration time. The sensor was deployed for field measurements of H2CO, and laboratory quantification of both formaldehyde and ethane are reported. A cross comparison of the atmospheric concentration data for H2CO with data collected by a collocated commercial H2CO sensor employing Hantzsch reaction based fluorometric detection was performed. These results show excellent agreement between these two different approaches for trace-gas quantification. In addition, laboratory experiments for dual gas quantification show accurate, fast response with no crosstalk between the two gas channels.

Chirped Laser Dispersion Spectroscopy for Remote Open-Path Trace-Gas Sensing

In this paper we present a prototype instrument for remote open-path detection of nitrous oxide. The sensor is based on a 4.53 μm quantum cascade laser and uses the chirped laser dispersion spectroscopy (CLaDS) technique for molecular concentration measurements. To the best of our knowledge this is the first demonstration of open-path laser-based trace-gas detection using a molecular dispersion measurement. The prototype sensor achieves a detection limit down to the single-ppbv level and exhibits excellent stability and robustness. The instrument characterization, field deployment performance, and the advantages of applying dispersion sensing to sensitive trace-gas detection in a remote open-path configuration are presented.

Broadband quantum cascade laser gain medium based on a “continuum-to-bound” active region design

We present quantum cascade laser designs at 7–9 μm with two lower injector states strongly coupled with the upper laser state at the operating electric fields. Optical transitions from these three coupled states contribute to a large gain spectrum width (∼250 cm−1 full width at half maximum), which enables external cavity tuning of the lasers over 200 cm−1. Lasers show comparable performance to the conventional narrow band design at a similar wavelength with a peak modal gain coefficient of ∼10 kA/cm, a slope efficiency ∼1 W/A, and good temperature performance (T0=170 K) in pulsed mode operation at 295 K.

Direct In Situ Quantification of HO2 from a Flow Reactor

The first direct in situ measurements of hydroperoxyl radical (HO2) at atmospheric pressure from the exit of a laminar flow reactor have been carried out using mid-infrared Faraday rotation spectroscopy. HO2 was generated by oxidation of dimethyl ether, a potential renewable biofuel with a simple molecular structure but rich low-temperature oxidation chemistry. On the basis of the results of nonlinear fitting of the experimental data to a theoretical spectroscopic model, the technique offers an estimated sensitivity of <1 ppmv over a reactor exit temperature range of 398-673 K. Accurate in situ measurement of this species will aid in quantitative modeling of low-temperature and high-pressure combustion kinetics.