Ultra-broadband spectroscopy using a 2-11.5 µm IDFG-based supercontinuum source.

Supercontinuum sources based on intrapulse difference frequency generation (IDFG) from mode-locked lasers open new opportunities in mid-infrared gas spectroscopy. These sources provide high power and ultra-broadband spectral coverage in the molecular fingerprint region with very low relative intensity noise. Here, we demonstrate the performance of such a light source in combination with a multipass cell and a custom-built Fourier transform spectrometer (FTS) for multispecies trace gas detection. The light source provides a low-noise, ultra-broad spectrum from 2-11.5 µm with ∼3 W output power, outperforming existing mid-infrared supercontinuum sources in terms of noise, spectral coverage, and output power. This translates to an excellent match for spectroscopic applications, establishing (sub-)ppb sensitivity for molecular hydrocarbons (e.g., CH4, C2H4), oxides (e.g., SO2, NOx), and small organic molecules (e.g., acetone, ethyl acetate) over the spectral range of the supercontinuum source with a measurement time varying from seconds to minutes. We demonstrate a practical application by measuring the off-gas composition of a bioreactor containing an acidic ammonia-oxidizing culture with the simultaneous detection of multiple nitrogen oxides (NO, NO2, N2O, etc.). As the different species absorb various parts of the spectrum, these results highlight the functionality of this spectroscopic system for biological and environmental applications.

Real-Time Measurement of CH4 in Human Breath Using a Compact CH4/CO2 Sensor.

The presence of an elevated amount of methane (CH4) in exhaled breath can be used as a non-invasive tool to monitor certain health conditions. A compact, inexpensive and transportable CH4 sensor is thus very interesting for this purpose. In addition, if the sensor is also able to simultaneously measure carbon dioxide (CO2), one can extract the end-tidal concentration of exhaled CH4. Here, we report on such a sensor based on a commercial detection module using tunable diode laser absorption spectroscopy. It was found that the measured CH4/CO2 values exhibit a strong interference with water vapor. Therefore, correction functions were experimentally identified and validated for both CO2 and CH4. A custom-built breath sampler was developed and tested with the sensor for real-time measurements of CH4 and CO2 in exhaled breath. As a result, the breath sensor demonstrated the capability of accurately measuring the exhaled CH4 and CO2 profiles in real-time. We obtained minimum detection limits of ~80 ppbv for CH4 and ~700 ppmv for CO2 in 1.5 s measurement time.

Fourier transform and grating-based spectroscopy with a mid-infrared supercontinuum source for trace gas detection in fruit quality monitoring.

We present a multi-species trace gas sensor based on a fast, compact home-built Fourier transform spectrometer (FTS) combined with a broadband mid-infrared supercontinuum (SC) source. The spectrometer covers the spectral bandwidth of the SC source (2 - 4 µm) and provides a best spectral resolution of 1 GHz in 6 seconds. It has a detection sensitivity of a few hundred of ppbv Hz-1/2 for different gas species. We study the performance of the developed spectrometer in terms of precision, linearity, long-term stability, and multi-species detection. We use the spectrometer for measuring fruit-produced volatiles under different atmospheric conditions and compare the performance with a previously developed scanning grating-based spectrometer.

Sensitive and broadband measurement of dispersion in a cavity using a Fourier transform spectrometer with kHz resolution: erratum.

We correct the values of the group delay dispersion of the cavity mirrors and N2, as well as the concentration of CO2, obtained from the measurement of the center frequencies of cavity modes using a comb-based Fourier transform spectrometer. The corrected values of group delay dispersion are a factor of 3 higher, which implies that the precision and accuracy of the dispersion measurements is 0.3 fs2 and 3 fs2, respectively.

Sensitive multi-species trace gas sensor based on a high repetition rate mid-infrared supercontinuum source.

We present a multi-species trace gas sensor based on a high-repetition-rate mid-infrared supercontinuum source, in combination with a 30 m multipass absorption cell, and a scanning grating spectrometer. The output of the spectrometer is demodulated by a digital lock-in amplifier, referenced to the repetition rate of the supercontinuum source. This improved the detection sensitivity of the system by a factor 5, as compared to direct baseband operation. The spectrometer provides a spectral coverage of 950 cm-1 (between 2.85-3.90 µm) with a resolution of 2.5 cm-1 in 100 ms. It can achieve noise equivalent detection limits in the order of 100 ppbv Hz-1/2 for various hydrocarbons, alcohols, and aldehydes.

Broadband Time-Resolved Absorption and Dispersion Spectroscopy of Methane and Ethane in a Plasma Using a Mid-Infrared Dual-Comb Spectrometer.

Conventional mechanical Fourier Transform Spectrometers (FTS) can simultaneously measure absorption and dispersion spectra of gas-phase samples. However, they usually need very long measurement times to achieve time-resolved spectra with a good spectral and temporal resolution. Here, we present a mid-infrared dual-comb-based FTS in an asymmetric configuration, providing broadband absorption and dispersion spectra with a spectral resolution of 5 GHz (0.18 nm at a wavelength of 3333 nm), a temporal resolution of 20 µs, a total wavelength coverage over 300 cm-1 and a total measurement time of ~70 s. We used the dual-comb spectrometer to monitor the reaction dynamics of methane and ethane in an electrical plasma discharge. We observed ethane/methane formation as a recombination reaction of hydrocarbon radicals in the discharge in various static and dynamic conditions. The results demonstrate a new analytical approach for measuring fast molecular absorption and dispersion changes and monitoring the fast dynamics of chemical reactions over a broad wavelength range, which can be interesting for chemical kinetic research, particularly for the combustion and plasma analysis community.

Mid-infrared supercontinuum-based upconversion detection for trace gas sensing.

Recent advancements of mid-infrared (MIR) supercontinuum light sources have opened up new possibilities in laser-based trace gas sensing. While the supercontinuum sources inherently support wide spectral coverage, the detection of broadband absorption signals with high speed and low cost is traditionally limited by the MIR detector arrays. In this work, we demonstrate that this limitation can be circumvented by upconverting the MIR signal into the near-infrared (NIR) region, where cost-effective silicon-based detector arrays can be utilized to measure broadband absorption. We also show that, by combining a MIR supercontinuum source with a MIR-to-NIR upconverter and an astigmatic multipass cell, fast detection (~20 ms) of ethane with sub-ppmv sensitivity can be achieved at room temperature. For multi-species detection, a least-square global fitting method is presented, showing a promising potential for applications such as environmental monitoring and biomedical research.

A Broadband Mid-Infrared Trace Gas Sensor Using Supercontinuum Light Source: Applications for Real-Time Quality Control for Fruit Storage.

We present a fully integrated and transportable multi-species trace gas sensor based on a mid-infrared (MIR) supercontinuum light source. The high brightness (surpassing synchrotron) and ultra-broad spectral bandwidth (2-4 µm) of this light source allows simultaneous detection of multiple broadband absorbing gas species. High sensitivity in the sub-ppmv level has been achieved by utilizing an astigmatic multipass cell. A grating-based spectrometer at a scanning rate of 20 Hz is developed employing a balanced detection scheme. A multi-component global fitting algorithm is implemented into a central LabVIEW program to perform real-time data analysis. The obtained concentration values are validated by the standard gas chromatography mass spectrometry (GC-MS) method. Field application of the sensor for quality control of stored fruits at a small scale is demonstrated, involving the detection of ethylene, ethanol, ethyl acetate, acetaldehyde, methanol, acetone, and water simultaneously. The sensor also shows promising potentials for other applications, such as environmental monitoring and biomedical research.

Laser spectroscopy for breath analysis: towards clinical implementation.

Detection and analysis of volatile compounds in exhaled breath represents an attractive tool for monitoring the metabolic status of a patient and disease diagnosis, since it is non-invasive and fast. Numerous studies have already demonstrated the benefit of breath analysis in clinical settings/applications and encouraged multidisciplinary research to reveal new insights regarding the origins, pathways, and pathophysiological roles of breath components. Many breath analysis methods are currently available to help explore these directions, ranging from mass spectrometry to laser-based spectroscopy and sensor arrays. This review presents an update of the current status of optical methods, using near and mid-infrared sources, for clinical breath gas analysis over the last decade and describes recent technological developments and their applications. The review includes: tunable diode laser absorption spectroscopy, cavity ring-down spectroscopy, integrated cavity output spectroscopy, cavity-enhanced absorption spectroscopy, photoacoustic spectroscopy, quartz-enhanced photoacoustic spectroscopy, and optical frequency comb spectroscopy. A SWOT analysis (strengths, weaknesses, opportunities, and threats) is presented that describes the laser-based techniques within the clinical framework of breath research and their appealing features for clinical use.

Sensitive Spectroscopy of Acetone Using a Widely Tunable External-Cavity Quantum Cascade Laser.

We employed a single-mode, widely tunable (~300 cm−1) external-cavity quantum cascade laser operating around 8 µm for broadband direct absorption spectroscopy and wavelength modulation spectroscopy where a modulation frequency of 50 kHz was employed with high modulation amplitudes of up to 10 GHz. Using a compact multipass cell, we measured the entire molecular absorption band of acetone at ~7.4 µm with a spectral resolution of ~1 cm−1. In addition, to demonstrate the high modulation dynamic range of the laser, we performed direct absorption (DAS) and second harmonic wavelength modulation spectroscopy (WMS-2f) of the Q-branch peak of acetone molecular absorption band (HWHM ~10 GHz) near 1365 cm−1. With WMS-2f, a minimum detection limit of 15 ppbv in less than 10 s is achieved, which yields a noise equivalent absorption sensitivity of 1.9 × 10−8 cm−1 Hz−1/2.

Sensitive and broadband measurement of dispersion in a cavity using a Fourier transform spectrometer with kHz resolution.

Optical cavities provide high sensitivity to dispersion since their resonance frequencies depend on the index of refraction. We present a direct, broadband, and accurate measurement of the modes of a high finesse cavity using an optical frequency comb and a mechanical Fourier transform spectrometer with a kHz-level resolution. We characterize 16000 longitudinal cavity modes spanning 16 THz of bandwidth in terms of center frequency, linewidth, and amplitude. Using the center frequencies we retrieve the group delay dispersion of the cavity mirror coatings and pure N2 with 0.1 fs2 precision and 1 fs2 accuracy, as well as the refractivity of the 3ν1 + ν3 absorption band of CO2 with 5 × 10-12 precision. This opens up for broadband refractive index metrology and calibration-free spectroscopy of entire molecular bands.

Fourier transform and Vernier spectroscopy using an optical frequency comb at 3-5.4 µm.

We present a versatile mid-infrared frequency comb spectroscopy system based on a doubly resonant optical parametric oscillator tunable in the 3-5.4 µm range and two detection methods: a Fourier transform spectrometer (FTS) and a continuous-filtering Vernier spectrometer (CF-VS). Using the FTS with a multipass cell, we measure high precision broadband absorption spectra of CH4 at 3.3 µm and NO at 5.25 µm, the latter for the first time with comb spectroscopy, and we detect atmospheric species (CH4, CO, CO2, and H2O) in air in the signal and idler ranges. Multiline fitting yields minimum detectable concentrations of 10-20 ppb Hz-1/2 for CH4, NO, and CO. For the first time in the mid-infrared, we perform CF-VS using an enhancement cavity, a grating, and a single detector, and we measure the absorption spectrum of CH4 and H2O in ambient air at ∼3.3 µm, reaching a 40 ppb concentration detection limit for CH4 in 2 ms.

Cavity-enhanced optical frequency comb spectroscopy of high-temperature H2O in a flame.

We demonstrate near-infrared cavity-enhanced optical frequency comb spectroscopy of water in a premixed methane/air flat flame. The detection system is based on an Er:fiber femtosecond laser, a high finesse optical cavity containing the flame, and a fast-scanning Fourier transform spectrometer (FTS). High absorption sensitivity is obtained by the combination of a high-bandwidth two-point comb-cavity lock and auto-balanced detection in the FTS. The system allows recording high-temperature water absorption spectra with a resolution of 1 GHz and a bandwidth of 50 nm in an acquisition time of 0.4 s, with absorption sensitivity of 4.2 × 10(-9) cm(-1) Hz(-1/2) per spectral element.

Noise-immune cavity-enhanced optical frequency comb spectroscopy.

We present a new method of optical frequency comb spectroscopy that combines cavity enhancement with frequency modulation to obtain immunity to laser frequency-to-amplitude noise conversion by the cavity modes and, thus, high absorption sensitivity over a broad spectral range. A frequency comb is locked to a cavity with a free spectral range (FSR) equal to 4/3 times the repetition rate of the laser, and phase-modulated at a frequency equal to the cavity FSR. The transmitted light is analyzed by a Fourier transform spectrometer with a high bandwidth detector. Phase-sensitive detection of the interferogram yields a noise-immune cavity-enhanced optical frequency comb spectroscopy (NICE-OFCS) signal. In the first demonstration, we record NICE-OFCS signals from the overtone CO2 band at 1575 nm with absorption sensitivity of 4.3×10(-10) cm(-1) Hz(-1/2) per spectral element, close to the shot noise limit.

Time-resolved mid-infrared dual-comb spectroscopy.

Dual-comb spectroscopy can provide broad spectral bandwidth and high spectral resolution in a short acquisition time, enabling time-resolved measurements. Specifically, spectroscopy in the mid-infrared wavelength range is of particular interest, since most of the molecules have their strongest rotational-vibrational transitions in this "fingerprint" region. Here we report time-resolved mid-infrared dual-comb spectroscopy, covering ~300 nm bandwidth around 3.3 µm with 6 GHz spectral resolution and 20 µs temporal resolution. As a demonstration, we study a CH4/He gas mixture in an electric discharge, while the discharge is modulated between dark and glow regimes. We simultaneously monitor the production of C2H6 and the vibrational excitation of CH4 molecules, observing the dynamics of both processes. This approach to broadband, high-resolution, and time-resolved mid-infrared spectroscopy provides a new tool for monitoring the kinetics of fast chemical reactions, with potential applications in various fields such as physical chemistry and plasma/combustion analysis.