Atmospheric Measurement Techniques (Mar 2010)
Characterizing a Quantum Cascade Tunable Infrared Laser Differential Absorption Spectrometer (QC-TILDAS) for measurements of atmospheric ammonia
Abstract
A compact, fast-response Quantum Cascade Tunable Infrared Laser Differential Absorption Spectrometer (QC-TILDAS) for measurements of ammonia (NH<sub>3</sub>) has been evaluated under both laboratory and field conditions. Absorption of radiation from a pulsed, thermoelectrically cooled QC laser occurs at reduced pressure in a 0.5 L multiple pass absorption cell with an effective path length of 76 m. Detection is achieved using a thermoelectrically-cooled Mercury Cadmium Telluride (HgCdTe) infrared detector. A novel sampling inlet was used, consisting of a short, heated, quartz tube with a hydrophobic coating to minimize the adsorption of NH<sub>3</sub> to surfaces. The inlet contains a critical orifice that reduces the pressure, a virtual impactor for separation of particles, and additional ports for delivering NH<sub>3</sub>-free background air and calibration gas standards. The level of noise in this instrument has been found to be 0.23 ppb at 1 Hz. The sampling technique has been compared to the results of a conventional lead salt Tunable Diode Laser Absorption Spectrometer (TDLAS) during a laboratory intercomparison. The effect of humidity and heat on the surface interaction of NH<sub>3</sub> with sample tubing was investigated at mixing ratios ranging from 30–1000 ppb. Humidity was seen to worsen the NH<sub>3</sub> time response and considerable improvement was observed when using a heated sampling line. A field intercomparison of the QC-TILDAS with a modified Thermo 42CTL chemiluminescence-based analyzer was also performed at Environment Canada's Centre for Atmospheric Research Experiments (CARE) in the rural town of Egbert, ON between May–July 2008. Background tests and calibrations using two different permeation tube sources and an NH<sub>3</sub> gas cylinder were regularly carried out throughout the study. Results indicate a very good correlation at 1 min time resolution (<i>R</i><sup>2</sup> = 0.93) between the two instruments at the beginning of the study, when regular background subtraction was applied to the QC-TILDAS. An overall good correlation of <i>R</i><sup>2</sup> = 0.85 was obtained over the entire two month data set, where the majority of the spread can be attributed to differences in inlet design and background subtraction methods.
