Alan Lim

Real-time monitoring of benzene, toluene, and p-xylene in a photoreaction chamber with a tunable mid-infrared laser and ultraviolet differential optical absorption spectroscopy

We describe the implementation of a mid-infrared laser-based trace gas sensor with a photoreaction chamber, used for reproducing chemical transformations of benzene, toluene, and p-xylene (BTX) gases that may occur in the atmosphere. The system performance was assessed in the presence of photoreaction products including aerosol particles. A mid-infrared external cavity quantum cascade laser (EC-QCL)-tunable from 9.41-9.88 μm (1012-1063 cm(-1))-was used to monitor gas phase concentrations of BTX simultaneously and in real time during chemical processing of these compounds with hydroxyl radicals in a photoreaction chamber. Results are compared to concurrent measurements using ultraviolet differential optical absorption spectroscopy (UV DOAS). The EC-QCL based system provides quantitation limits of approximately 200, 200, and 600 parts in 10(9) (ppb) for benzene, toluene, and p-xylene, respectively, which represents a significant improvement over our previous work with this laser system. Correspondingly, we observe the best agreement between the EC-QCL measurements and the UV DOAS measurements with benzene, followed by toluene, then p-xylene. Although BTX gas-detection limits are not as low for the EC-QCL system as for UV DOAS, an unidentified by-product of the photoreactions was observed with the EC-QCL, but not with the UV DOAS system.

Detection of benzene and toluene gases using a midinfrared continuous-wave external cavity quantum cascade laser at atmospheric pressure

We demonstrate the application of a commercially available widely tunable continuous-wave external cavity quantum cascade laser as a spectroscopic source for the simultaneous detection of multiple gases. We measured broad absorption features of benzene and toluene between 1012 and 1063 cm(-1) (9.88 and 9.41 microm) at atmospheric pressure using an astigmatic Herriott multipass cell. Our results show experimental detection limits of 0.26 and 0.41 ppm for benzene and toluene, respectively, with a 100 m path length for these two gases.

Off-axis cavity enhanced spectroscopy based on a pulsed quantum cascade laser for sensitive detection of ammonia and ethylene

A pulsed, distributed feedback (DFB) quantum cascade (QC) laser centered at 970 cm(-1) was used in combination with an off-axis cavity enhanced absorption (CEA) spectroscopic technique for the detection of ammonia and ethylene. Here, the laser is coupled into a high-finesse cavity with an optical path length of ∼76 m. The cavity is installed into a 53 cm long sample cell with a volume of 0.12 L. The laser is excited with short current pulses (5-10 ns), and the pulse amplitude is modulated with an external current ramp, resulting in a ∼0.3 cm(-1) frequency scan. A demodulation approach followed by numerical filtering was utilized to improve the signal-to-noise ratio. We demonstrated detection limits of ~15 ppb and ∼20 ppb for ammonia and ethylene, respectively, with less than 5 s averaging time.

Wavelength modulation spectroscopy with a pulsed quantum cascade laser for the sensitive detection of acrylonitrile

A pulsed, distributed feedback (DFB) quantum cascade laser centered at 957 cm−1 was used in combination with a wavelength modulation spectroscopic technique for the detection of acrylonitrile. The laser was excited with short current pulses (5–10 ns), and the pulse amplitude was modulated with a linear subthreshold current ramp at 20 Hz resulting in a ∼2.5 cm−1 frequency scan. This allowed the measurement of spectroscopic features of acrylonitrile with absorption line widths of ∼1 cm−1. A demodulation approach followed by numerical filtering was utilized to improve the signal-to-noise ratio. We then superimposed a 10 kHz sine wave current modulation on top of the 20 Hz current ramp. The resulting high frequency temperature modulation of the DFB structure results in wavelength modulation. A minimum detectable absorbance of ∼10−5, corresponding to the sub 109 levels of acrylonitrile, was achieved with less than a minute averaging time.

New concept design of differential absorption LIDAR : fusion of DIAL and TDLS methods

We propose a new approach to range-resolved remote gas sensing in the atmosphere based on a combination of a DIAL and tunable-laser diode spectroscopy (TDLS) methods. To add range-resolving capabilities to a TDLS sensor we propose to arrange a group of retroreflectors (RRs) dividing an absorption path into adjacent measurement sections similar to those utilized by conventional DIAL systems. We implemented two techniques for the interrogation of the RRs: 1) scanning a beam of a continuous-wave laser over RRs sequentially; 2) using a time delay between returns from different RRs illuminated with a pulsed laser. We employed scanning technique with a vertical-cavity surface-emitting laser (VCSEL) operating near 1389 nm. A single-pulse interrogation method was demonstrated with a 10.9-&mgr;m quantum cascade laser (QCL) suitable for detection of ammonia, ethylene and water vapor in the atmosphere. Gas sensing and ranging was performed over distances varying from ~ 1 m up to ~ 1 km. Using VCSEL we attained a 0.5-s time resolution in gas concentration profiling with a 10-cm spatial resolution. Minimum interrogation time of a group of RRs was ~ 9 ms. A new generation of differential absorption LIDARs can be developed for range-resolved gas sensing in the atmosphere over distances up to ~ 1 km. The instruments can be used for a variety of applications ranging from fencing industrial areas to monitor fluxes of atmospheric pollutants to continuous air quality control in populated areas

Monitoring Multiple Trace Gas Species during Secondary Organic Aerosol Formation in a Smog Simulation Chamber using Mid-IR Laser and UV Spectroscopic Methods

We demonstrate our progress in developing an application of mid-IR External Cavity Quantum Cascade Laser (EC-QCL) for concentration measurements of benzene, toluene, ethylbenzene and o- and p-xylene (BTEX) in a simulation chamber.

Wavelength modulation spectroscopy with a pulsed quantum cascade laser

A pulsed distributed feedback quantum cascade laser (QCL) operating near 957 cm-1 was employed in wavelength modulation mode for spectroscopic trace gas sensing applications. The laser was excited with short current pulses (5-10 ns) with < 2% duty cycle. The pulse amplitude was modulated with a linear sub-threshold current ramp at 20 Hz resulting in a ~ 2.5 cm-1 frequency scan, which is typically wider than what has been reported for these lasers, and would allow one to detect molecular absorption features with line widths up to 1 cm-1. A demodulation approach followed by numerical filtering was utilized to improve the signal-to-noise ratio. We then superimposed a sine wave current modulation at 10 kHz onto the 20 Hz current ramp. The resulting high frequency temperature modulation of the distributed feedback (DFB) structure results in wavelength modulation (WM). The set-up was tested by recording relatively weak absorption lines of carbon dioxide. We demonstrated a minimum detectable absorbance of 10-5 for this spectrometer. Basic instrument performance and optimization of the experimental parameters for sensitivity improvement are discussed.