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.

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.

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.

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