Over the past two decades mid-infrared laser spectroscopy has been increasingly utilized during airborne atmospheric
studies to improve our understanding of atmospheric processes and transformations. Enhancing such understanding
requires a suite of ever more sensitive, selective, versatile, and fast instruments that can measure trace atmospheric
constituents at and below mixing ratios of 100-parts-per-trillion-by-volume. Instruments that can carry out such
measurements are very challenging, as airborne platforms vibrate, experience accelerations, and undergo large swings in
cabin temperature and pressure. These challenges notwithstanding, scientists and engineers at the National Center for
Atmospheric Research (NCAR) have long been employing mid-infrared absorption spectroscopy to make atmospheric
measurements of important trace gases like formaldehyde (CH2O) on a variety of airborne platforms. The present paper
discusses a new airborne spectrometer based upon a difference frequency generation (DFG) mid-IR laser source that was
first deployed in 2006. Many of the fundamental components and concepts of this spectrometer closely follow those
incorporated in our liquid-nitrogen cooled tunable lead-salt diode laser system, successfully employed for airborne
CH2O measurements over the past 10 years. However, a number of significant modifications were incorporated in the
new DFG spectrometer and these will be briefly discussed here along with system performance. The DFG spectrometer
was recently deployed during the 2008 Arctic Research of the Composition of the Troposphere from Aircraft and
Satellites (ARCTAS) campaign, and specific examples of its performance from this study will be discussed, as will
prospects for the detection of other trace gases.
Tunable, mid-infrared lasers based on quasi-phase matched bulk PPLN crystals have successfully been
implemented on airborne atmospheric research platforms and enabling a detectable fractional absorbance of
about 5E-7, which equates to single digit part-per-trillion detectable concentrations for many atmospherically
important trace gases. Emerging development of ridge waveguide type PPLN crystals show promising
performance characteristics, including 100 times better conversion efficiency and good beam quality, which
enable more compact system designs. In addition, the flexibility afforded by QPM structured materials to
generate coherent mid-infrared radiation, permit unique multi-wavelength operation and detection techniques.
Enhancing our understanding of atmospheric processes and transformations require a suite of ever more sensitive,
selective, versatile, and fast instruments that can measure trace atmospheric constituents at and below mixing ratios of
100-parts-per-trillion on airborne platforms. Instruments that can carry out such measurements are very challenging, as
airborne platforms vibrate, experience accelerations, and undergo large swings in cabin temperatures and pressures.
These challenges notwithstanding, scientists and engineers at the National Center for Atmospheric Research (NCAR) in
collaboration with Rice University have long been employing mid-infrared absorption spectroscopy to acquire
atmospheric measurements of important trace gases like formaldehyde on a variety of airborne platforms. The present
paper will discuss two very recent airborne formaldehyde instruments employing tunable diode laser and difference
frequency generation mid-IR laser sources. Both instruments employ second-harmonic absorption spectroscopy utilizing
astigmatic multipass Herriott cells. This paper will discuss the performance of both instruments during recent airborne
campaigns, focusing on the many steps necessary for minimizing the various aircraft perturbations. Prospects for the
detection of other trace gases will also be presented.
Laser based gas detection and monitoring techniques have now evolved to a mature level. Critical laser performance parameters include spatial beam quality, usable IR power, linear frequency tunability and stability. For continuous-wave, long-path absorption spectroscopy, the development of robust mid-infrared spectroscopic sources has led to numerous selective, sensitive and real-time gas monitoring applications. These new compact and tunable spectroscopic sources (<0.5 cubic feet) can be designed for efficient room-temperature operation in the 2.4 - 4.6 microns wavelength region using standard near-IR telecom lasers that are optically mixed in nonlinear optical materials such as periodically poled LiNbO3 (PPLN). Wavelength multiplexing and flexible dispersion control of PPLN crystals offer convenient narrow-linewidth (100 kHz - 2 MHz), single or multiple-frequency mid-IR operation at the milli-watt level. This permits the sensitive detection of many molecules such as HF, HCl, CH2O, CH4, CO2, CO and N2O at their strong fundamental rotational-vibrational transitions using direct, dual-beam, 2-f and other advanced spectroscopic detection schemes. At this wavelength region, these new laser sources provide an ideal alternative to cryogenically cooled lead-salt diode lasers. This paper will focus on the comparison of the two technologies with an emphasis on achieving ultra-high sensitivity in ground and airborne applications.
Formaldehyde (CH2O) is a ubiquitous component of both the remote atmosphere as well as the polluted urban atmosphere. This important gas-phase intermediate is a primary emission product from hydrocarbon combustion sources as well as from oxidation of natural hydrocarbons emitted by plants and trees. Through its subsequent decomposition, formaldehyde is a source of reactive hydrogen radicals, which control the oxidation capacity of the atmosphere. Because ambient CH2O concentrations attain levels as high as several tens of parts-per-billion (ppbv) in urban areas to levels as low as tens of parts-per-trillion (pptv) in the remote background atmosphere, ambient measurements become quite challenging, particularly on airborne platforms. The present paper discusses an airborne tunable diode laser absorption spectrometer, which has been developed and refined over the past 6 years, for such demanding measurements. The results from a recent study will be presented.
KEYWORDS: Modulation, Quantum cascade lasers, Frequency modulation, Doppler effect, Fermium, Absorption, Amplitude modulation, Sensors, Spectroscopy, Signal to noise ratio
Inter-subband (Type I) quantum-cascade (QC) lasers have shown the potential to generate tunable mid-IR radiation with narrow intrinsic linewidths (< 160 KHz in 15 mSec sweeps) and excellent amplitude stability (< 3 ppm averaged over minutes). Our bench-scale efforts to develop the Type I distributed feedback (DFB)-QC lasers for fieldable atmospheric chemistry campaigns, where multipass (Herriot or White) cells are used to enhance path-length, have not yet realized performance to the low intrinsic noise levels seen in these devices. By comparison, many operational systems' levels of noise-equivalent-absorbance (NEA) using Pb-salt lasers can routinely achieve at least one-order of magnitude better cw-performance, and with much lower powers. We have found that instability effets from weak back-scattered laser light -primarily from the Herriot cell- results in feedback-implicated technical noise well above the thermal and shot-noise of standard IR detectors. Of more fundamental concern is the fact that planar-stripe DFB-QC lasers undergo beam steering and transverse spatial-mode competitions during current tuning. It is the development of fully automated sub-ppbV sensitive IR chem-sensors. It is possible to reach low-ppm levels of absorptance change-detection (ΔI/I0) over small wavelength regions with careful alignment to 100 M Herriott cells, but extreme care in spatial filtering is critical. However in the case of optical configurations which preclude significant optical feedback and need for stringent mode coupling alignments, the cw-DFB-QC lasers show great promise to do high resolution sub-Doppler spectroscopy. By serendipitous events, a varient of 'mode- or level-crossing' spectroscopy was probably rediscovered, which may allow very high resolution, sub-Doppler features and/or hyperfine alignments to be probed with 'uni-directional' topologies. We will primarily discuss the basic features of the 'uni-directional' sub-Doppler spectroscopy concept in this report. It shows potential to be exploitable in multi-pass cells or ring configurations. The phenomena of satuation 'dips' in molecular transitions appear to be very accessible with sinusoidally current-modulated DFB-QC lasers. Observations of sub-Doppler structures, either induced by residual AM 'pulsation dips' and/or hyperfine level-crossing effects (due to weak Zeeman splittings by the earth's B-field) can be recovered with good contrast. If this phenomena is indeed implicated with long-lived coherent hyperfine alignments, due perhaps to coherent population trapping in 'dark-states,' then sub-Doppler signals from saturated 'level-crossings' can potentially be seen without recourse to expensive polarization optics, nor elaborate beam shaping and isolation techniques.
The development of compact mid-IR sources using frequency- converted diode lasers has been demonstrated to be applicable for the ultra sensitive, selective, and real time detection of many trace gas species in the infrared spectroscopic fingerprint region, which contains virtually all the fundamental vibrational modes of molecules. This development of infrared laser sources has taken advantage of recent significant technological advances of semiconductor diode lasers and solid state lasers, new nonlinear optical materials, optical fiber and novel data acquisition techniques. Such sensors are able to detect molecules at the parts-per-billion level in ambient air using infrared absorption spectroscopy either by monitoring trace gases in an open path or multi-pass cell configuration. Real world applications ranging from urban, industrial, rural emission studies to spacecraft habitat monitoring are described.
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