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.
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.
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.
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.
Rapid and accurate ambient measurements of the tropospheric trace gas formaldehyde (CH2O) have been made by the NCAR low altitude tunable diode laser absorption spectrometer on both aircraft and ground based platforms. Field sensitivities of 80 - 120 pptv in 1 minute (40 - 60 pptv in 5 min) were typical of the first aircraft version of the instrument, providing good resolution for studying formaldehyde's role in the oxidative mechanisms of the troposphere. Recently the instrument has been modified to provide simultaneous detection of a second tropospherically interesting molecule, hydrogen peroxide (H2O2), as well as enhanced measurement precision and instrument stability. The optic assembly of the new Dual Channel Airborne Laser System (DCALS) has been designed to be more mechanically stable and better thermally conditioned. Other improvements include measures to mitigate optical noise, stabilize cell pressure, and minimize sample perturbation. Measurements of formaldehyde by DCALS at a ground site during the 1999 Southern Oxidants Study show improved sensitivities of 30 - 100 pptv in 1 minute, and much better long term instrument stability.
Accurate measurements of formaldehyde (CH2O), a trace gas found throughout the atmosphere, are important for furthering our understanding of hydrocarbon oxidation processes in the atmosphere. During the 1997 North Atlantic Regional Experiment numerous trace gases, including CH2O, were measured onboard a WP3 aircraft operated by the National Oceanic and Atmospheric Administration to study continental transport and photochemistry over remote regions of the North Atlantic Ocean. A highly sensitive tunable diode laser absorption spectrometer was employed in acquiring ambient CH2O measurements on 10 different flights during this campaign. A second instrument, based on chemical derivatization of ambient CH2O with DNPH, was also operated on the WP3 aircraft. This paper will briefly summarize the aircraft TDLAS system employed and discuss the level of agreement obtained between both instruments. This will be followed by a brief discussion of the results, and concludes with a preliminary comparison of the measurements with a 0-dimensional box model constrained by the measurements of other species during the campaign.
Highly sensitive and accurate measurements of numerous trace gases are required to further our understanding of atmospheric processes. Tunable diode laser systems, which offer many advantages in this regard, can be designed for reliable field measurements on both ground-based and aircraft platforms. The present paper describes the long term effort at the National Center for Atmospheric Research (NCAR) to develop, employ, and validate a highly sensitive tunable diode laser absorption spectrometer for the measurement of various trace gases, including formaldehyde and carbon monoxide. This system was successfully employed on three recent aircraft campaigns. The present paper describes the aircraft instrument along with hardware and software features incorporated for high sensitivity, with particular emphasis on major modifications to the NCAR aircraft system over the past year.
A time-resolved flash photolysis/tunable diode laser absorption spectroscopy system has been constructed to study reaction products of gas-phase chemical reactions. The use of FP to initiate the chemistry results in essentially a wall-less reactor due to the time of reaction being much shorter than the time of diffusion. The use of TDLAS allows the time-resolved detection of HCl by monitoring individual lines in the rovibrational spectrum. While the system is being developed for study of the products of radical-radical reactions, preliminary studies involved detection of HCl from reaction of Cl-atoms with organic species. The reaction Cl + C2H6 yields HCl + C2H5 (1) was studied to characterize the system and determine the detection limit for HCl. The rate coefficient, k1, was determined to be (5.9 +/- 0.4) X 10-11 cm3 molec-1s-1 in agreement with the recommended values. HCl (v equals 0) and HCl (V equals 1) were simultaneously measured as products of the reaction Cl + CH3CHO yields HCl + CH3CO (2) at 2906.247 cm-1 and 2906.337 cm-1 respectively. It was determined for this reaction that k2 equals (7.5 +/- 0.6) X 10-11 cm3molec-1s-1.
A ground based tunable diode laser absorption spectrometer (TDLAS) developed at NCAR for the measurement of formaldehyde (HCHO) has been modified for use aboard tropospheric aircraft. Measurements of HCHO are essential to comprehensive investigations of atmospheric oxidation processes, and aircraft platforms provide the advantage of vertically and spatially resolved measured. Initial deployment of the aircraft system occurred during the spring and summer of 1996 as part of the NARE and STERAO campaigns. Data coverage exceeded 95 percent out of a sum total of 175 flight hours. Sensitivities achieved during STERAO were approximately 40-60 pptv for 4.5 min of measurement and 80- 120 pptv for 55s; NARE sensitivities were slightly worse. For both campaigns, post-flight fitting of background spectra indicated periodic outgassing and contamination of the background matrix air. Analysis of data collected during the May 1995 SOS intercomparison suggests that background subtraction largely nullifies any outgassing effect. Background matrix gas HCHO concentrations were determined by fitting background spectra and were then used to correct the associated ambient data sets. Finally, fits of the difference of successive backgrounds appear to approximate measurement replicate precisions and are more informative than calculated fit precisions.
Formaldehyde (HCHO) is an important reactive intermediate in atmospheric studies. Accurate measurements of HCHO are required to constrain and validate photochemical models. Despite this importance, there is still considerable uncertainty in present ambient measurements of this gas as well as in measurement-model relationships. The present paper discusses the long-term effort at NCAR to develop, employ, and validate a highly sensitive tunable diode laser absorption spectrometer (TDLAS) for ambient measurements of HCHO. A detailed analysis of measurement precision will be presented and performance improvements using rapid background subtraction, FFT filtering, and scan-by-scan demeaning will be discussed. This paper will conclude with a brief discussion of recent photochemistry and intercomparison field campaigns employing the TDLAS.
The technique of tunable diode laser absorption spectroscopy offers many advantages such as high selectivity, sensitivity, and versatility, in measuring trace atmospheric species in both the laboratory and field. In this paper, we present research activities at the National Center for Atmospheric Research employing this technique for studies of the earth's troposphere and stratosphere.
In this paper, we describe a new field diode laser system which incorporates a commercially-available astigmatic Herriott cell. This cell achieves a path length of 100 m while retaining a relative small sampling volume (approximately 3 l). This combination allows both high sensitivity and low cell residence times to be achieved. The optical system for effectively coupling the diode laser radiation into such a cell is briefly discussed. Line fitting procedures are also discussed for fitting second harmonic spectra in the presence of sloping and/or curved baseline structure. An initial application using the filed system for detection of formaldehyde is also described. Initial estimates place the instrumental detection sensitivity at approximately 50 pptv for formaldehyde using a 1Hz sampling bandwidth. This corresponds to a minimum detectable absorbance of about 2X10-6.
The stratospheric aerosol sulfate layer (Junge layer) may influence the earth's radiation budget, climate, and stratospheric ozone levels. In this paper, we present research activities at the National Center for Atmospheric Research employing high resolution tunable diode laser absorption spectroscopy which address two separate aspects of the Junge layer: laboratory heterogeneous measurements of reaction probabilities between stratospheric gases of importance and aqueous H2SO4 aerosols, and studies of OCS sources, sinks, and potential long-term secular trends.
The ambient fluctuations of long-lived atmospheric gases such as carbon dioxide, methane, and carbonyl sulfide, to name a few, contain important information about sources, sinks and potential secular trends. Since such fluctuations can be quite small, typically less than a few percent, high precision instruments are required. In the present study, we describe a versatile tunable diode laser system for this purpose. This system employs a number of novel features for increased system control and versatility. In addition to high precision, such versatility enables us to acquire the ratio of 2 spectral features with high precision, even when the signal amplitudes are a factor of 26 different and when the spectral features are separated by as much as 0.424 cm-1. This capability can be used to address many important applications in atmospheric studies.
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