We present a practical implementation of calibration-free wavelength-modulation spectroscopy with second harmonic detection (WMS-2f) for measurements of gas temperature and concentration in harsh environments. The method is applicable to measurements using lasers with synchronous wavelength and intensity modulation (such as injection current-tuned diode lasers). The key factors that enable measurements without the on-site calibration normally associated with WMS are (1) normalization of the WMS-2f signal by the first harmonic (1f) signal to account for laser intensity, and (2) the inclusion of laser-specific tuning characteristics in the spectral-absorption model that is used to compare with measured 1f-normalized, WMS-2f signals to infer gas properties. The uncertainties associated with the calibration-free WMS method are discussed, with particular emphasis on the influence of pressure and optical depth on the WMS signals. Many of these uncertainties are also applicable to calibrated WMS measurements. An example experimental setup that combines six tunable diode laser sources between 1.3 and 2.0 mum into one probe beam for measurements of temperature, H(2)O, and CO(2) is shown. A hybrid combination of wavelength and frequency demultiplexing is used to distinguish among the laser signals, and the optimal set of laser-modulation waveforms is presented. The system is demonstrated in the harsh environment of a ground-test scramjet combustor. A comparison of direct absorption and 1f-normalized, WMS-2f shows a factor of 4 increase in signal-to-noise ratio with the WMS technique for measurements of CO(2) in the supersonic flow. Multidimensional computational fluid-dynamics (CFD) calculations are compared with measurements of temperature and H(2)O using a simple method that accounts for the influence of line-of-sight (LOS) nonuniformity on the absorption measurements. The comparisons show the ability of the LOS calibration-free technique to gain useful information about multidimensional CFD models.

Tunable diode laser absorption measurements at high pressures by use of wavelength-modulation spectroscopy (WMS) require large modulation depths for optimum detection of molecular absorption spectra blended by collisional broadening or dense spacing of the rovibrational transitions. Diode lasers have a large and nonlinear intensity modulation when the wavelength is modulated over a large range by injection-current tuning. In addition to this intensity modulation, other laser performance parameters are measured, including the phase shift between the frequency modulation and the intensity modulation. Following published theory, these parameters are incorporated into an improved model of the WMS signal. The influence of these nonideal laser effects is investigated by means of wavelength-scanned WMS measurements as a function of bath gas pressure on rovibrational transitions of water vapor near 1388 nm. Lock-in detection of the magnitude of the 2f signal is performed to remove the dependence on detection phase. We find good agreement between measurements and the improved model developed for the 2f component of the WMS signal. The effects of the nonideal performance parameters of commercial diode lasers are especially important away from the line center of discrete spectra, and these contributions become more pronounced for 2f signals with the large modulation depths needed for WMS at elevated pressures.

Identification and quantification of trace gas sources is a major challenge for understanding and regulating air quality and greenhouse gas emissions. Current approaches either provide continuous but localized monitoring, or quasi-instantaneous "snapshot-in-time" regional monitoring. There is a need for emissions detection that provides both continuous and regional coverage, because sources and sinks can be episodic and spatially variable. We field deploy a dual frequency comb laser spectrometer for the first time, enabling an observing system that provides continuous detection of trace gas sources over multiple-square-kilometer regions. Field tests simulating methane emissions from oil and gas production demonstrate detection and quantification of a 1.6 g min -1 source (approximate emissions from a small pneumatic valve) from a distance of 1 km, and the ability to discern two leaks among a field of many potential sources. The technology achieves the goal of detecting, quantifying, and attributing emissions sources continuously through time, over large areas, and at emissions rates ~1000x lower than current regional approaches. It therefore provides a useful tool for monitoring and mitigating undesirable sources and closes a major information gap in the atmospheric sciences.

Tunable diode laser absorption measurements of gas temperature and water concentration were made at the exit of a model scramjet combustor fueled on JP-7. Multiplexed, fiber-coupled, near-infrared distributed feedback lasers were used to probe three water vapor absorption features in the 1.34-1.47 microm spectral region (2v1 and vl + v3 overtone bands). Ratio thermometry was performed using direct-absorption wavelength scans of isolated features at a 4-kHz repetition rate, as well as 2f wavelength modulation scans at a 2-kHz scan rate. Large signal-to-noise ratios demonstrate the ability of the optimally engineered optical hardware to reject beam steering and vibration noise. Successful measurements were made at full combustion conditions for a variety of fuel/air equivalence ratios and at eight vertical positions in the duct to investigate spatial uniformity. The use of three water vapor absorption features allowed for preliminary estimates of temperature distributions along the line of sight. The improved signal quality afforded by 2f measurements, in the case of weak absorption, demonstrates the utility of a scanned wavelength modulation strategy in such situations.

Abstract. We present the first quantitative intercomparison between two open-path dual-comb spectroscopy (DCS) instruments which were operated across adjacent 2 km openair paths over a 2-week period. We used DCS to measure the atmospheric absorption spectrum in the near infrared from 6023 to 6376 cm −1 (1568 to 1660 nm), corresponding to a 355 cm −1 bandwidth, at 0.0067 cm −1 sample spacing. The measured absorption spectra agree with each other to within 5 × 10 −4 in absorbance without any external calibration of either instrument. The absorption spectra are fit to retrieve path-integrated concentrations for carbon dioxide (CO 2 ), methane (CH 4 ), water (H 2 O), and deuterated water (HDO). The retrieved dry mole fractions agree to 0.14 % (0.57 ppm) for CO 2 , 0.35 % (7 ppb) for CH 4 , and 0.40 % (36 ppm) for H 2 O at ∼ 30 s integration time over the 2-week measurement campaign, which included 24 • C outdoor temperature variations and periods of strong atmospheric turbulence. This agreement is at least an order of magnitude better than conventional active-source open-path instrument intercomparisons and is particularly relevant to future regional flux measurements as it allows accurate comparisons of open-path DCS data across locations and time. We additionally compare the open-path DCS retrievals to a World Meteorological Organization (WMO)-calibrated cavity ring-down point sensor located along the path with good agreement. Shortterm and long-term differences between the open-path DCS and point sensor are attributed, respectively, to spatial sampling discrepancies and to inaccuracies in the current spectral database used to fit the DCS data. Finally, the 2-week measurement campaign yields diurnal cycles of CO 2 and CH 4 that are consistent with the presence of local sources of CO 2 and absence of local sources of CH 4 .