Rafal Lewicki

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 ppb-level detection of CO and N2O using a high power CW DFB-QCL.

An ultra-sensitive and selective quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor platform was demonstrated for detection of carbon monoxide (CO) and nitrous oxide (N2O). This sensor used a state-of-the art 4.61 μm high power, continuous wave (CW), distributed feedback quantum cascade laser (DFB-QCL) operating at 10°C as the excitation source. For the R(6) CO absorption line, located at 2169.2 cm(-1), a minimum detection limit (MDL) of 1.5 parts per billion by volume (ppbv) at atmospheric pressure was achieved with a 1 sec acquisition time and the addition of 2.6% water vapor concentration in the analyzed gas mixture. For the N2O detection, a MDL of 23 ppbv was obtained at an optimum gas pressure of 100 Torr and with the same water vapor content of 2.6%. In both cases the presence of water vapor increases the detected CO and N2O QEPAS signal levels as a result of enhancing the vibrational-translational relaxation rate of both target gases. Allan deviation analyses were performed to investigate the long term performance of the CO and N2O QEPAS sensor systems. For the optimum data acquisition time of 500 sec a MDL of 340 pptv and 4 ppbv was obtained for CO and N2O detection, respectively. To demonstrate reliable and robust operation of the QEPAS sensor a continuous monitoring of atmospheric CO and N2O concentration levels for a period of 5 hours were performed.

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.

Ppb-level detection of nitric oxide using an external cavity quantum cascade laser based QEPAS sensor

Geometrical parameters of micro-resonator for a quartz enhanced photoacoustic spectroscopy sensor are optimized to perform sensitive and background-free spectroscopic measurements using mid-IR quantum cascade laser (QCL) excitation sources. Such an optimized configuration is applied to nitric oxide (NO) detection at 1900.08 cm(-1) (5.26 µm) with a widely tunable, mode-hop-free external cavity QCL. For a selected NO absorption line that is free from H(2)O and CO(2) interference, a NO detection sensitivity of 4.9 parts per billion by volume is achieved with a 1-s averaging time and 66 mW optical excitation power. This NO detection limit is determined at an optimal gas pressure of 210 Torr and 2.5% of water vapor concentration. Water is added to the analyzed mixture in order to improve the NO vibrational-translational relaxation process.

A Mid-infrared QEPAS sensor device for TATP detection

Recent developments of external cavity quantum cascade lasers (EC-QC lasers) enable new applications in laser spectroscopy of trace gas species in the mid-infrared spectral region. We report the application of quartz enhanced photo acoustic spectroscopy (QEPAS) with widely tuneable EC-QC lasers as excitation sources for chemical sensing of different species such as triacetone triperoxide (TATP). A pulsed EC-QC laser operating at v~1120cm-1 and a cw EC-QC laser operating at v~950cm-1 are used for the detection of the explosive TATP which is a mid infrared broad band absorber. The detection limit of our present setup is ~1ppm TATP at atmospheric pressure.

Real time ammonia detection in exhaled human breath with a quantum cascade laser based sensor

Quantum cascade laser based breath sensor platform for medical applications employing a quartz-enhanced photoacoustic spectroscopy technique is reported. The detection sensitivity for exhaled ammonia is at ≪10 ppbv level with 1 s time resolution.

Recent advances and applications of mid-infrared based trace gas sensor technology

Recent advances in the development of sensors based on infrared quantum cascade lasers for the detection of trace gas species is reported. Several selected examples of applications in environmental and industrial process monitoring as well as in medical diagnostics using quartz enhanced photoacoustic spectroscopy and laser absorption spectroscopy will be described.

Faraday rotation spectroscopy of nitrogen dioxide based on a widely tunable external cavity quantum cascade laser

Faraday Rotation Spectroscopy (FRS) is a technique for the sensitive and selective detection of paramagnetic molecules or radicals such as NO, NO2, O2 or OH-. Moreover FRS is suitable for atmospheric measurements due to the insensitivity to non-paramagnetic interfering molecules such as H2O and CO2. Experimental results of an FRS sensor for the NO2detection employing an external-cavity quantum cascade laser (EC-QCL) are reported. The CW EC-QCL exhibits modehop free (MHF) tuning between 1600 cm-1 and 1650 cm-1. This allows targeting the optimum 441←440 Q-branch NO2transition at 1613.25 cm-1. A rotation of the polarization state of the initially linearly polarized laser light is observed when an AC magnetic field is applied to the NO2 cell, placed between two nearly crossed Rochon polarizers. This rotation of the polarization state is proportional to the NO2 concentration and can be determined by a photodetector located after the second polarizer. For long-term continuous measurements a second branch consisting of a detector and reference cell filled with 0.2 % NO2 in N2 is used to lock the laser to the selected NO2 transition. A minimum detection sensitivity (1σ) of 1 parts per billion (ppbv) was obtained for a 1 sec lock-in time constant (TC).

Sensitive detection of nitric oxide using a 5.26 μm external cavity quantum cascade laser based QEPAS sensor

The development and performance of a continuous wave (CW), thermoelectrically cooled (TEC) external cavity quantum cascade laser (EC-QCL) based sensor for quantitative measurements of nitric oxide (NO) concentrations in exhaled breath will be reported. Human breath contains ~ 400 different chemical species, usually at ultra low concentration levels, which can serve as biomarkers for the identification and monitoring of human diseases or wellness states. By monitoring exhaled NO concentration levels, a fast non-invasive diagnostic method for treatment of patients with asthma and chronic obstructive pulmonary disease (COPD) is feasible. The NO concentration measurements are performed with a 2f wavelength modulation based quartz enhanced photoacoustic spectroscopy (QEPAS) technique, which is very suitable for real time breath measurements, due to the fast gas exchange inside a compact QEPAS gas cell (<5 mm3 typical volume). In order to target the optimal interference free NO R (6.5) absorption doublet at 1900.08 cm-1(λ~5.263 μm) a Daylight Solutions Inc. widely tunable, mode-hop free 100 mW EC-QCL was used. The sensor reference channel includes a 10 cm long reference cell, filled with a 0.5% NO in N2 at 150 Torr, which is used for line-locking purpose. A minimum detection limit (1σ) for the EC-QCL based line locked NO sensor is ~5 ppbv with a 1 sec update time by a custom built control QCL compatible electronics unit.