Rapid Detection of Volatile Organic Compounds by Switch-Scan Tuning of Vernier Quantum-Cascade Lasers.

Volatile organic compounds (VOCs) exhibit typically broad and mutually overlapping ro-vibrational absorption fingerprints. This complexity has so far limited the applicability of laser-based spectroscopy for VOC measurements in complex gas matrices. Here, we exploit a Vernier-type quantum-cascade laser (QCL) as an electrically tunable multiwavelength source for selective and sensitive VOC analysis. This emerging class of lasers provides access to several spectral windows by discrete Vernier tuning ("switching") and continuous coverage within these windows ("scanning"). We present a versatile driving technique that efficiently combines the two tuning mechanisms. Applied to our Vernier QCL, it enables the rapid acquisition (within 360 ms) of high-resolution spectra from six individual spectral windows, distributed over a wide range from 1063 to 1102 cm-1. Gaining access to the broad absorption envelopes of VOCs at multiple frequencies, along with their superimposed fine structure, which are especially pronounced at a reduced sample pressure, offers completely new opportunities in VOC analysis. The potential of this approach is assessed in a direct-laser-absorption setup with acetaldehyde, ethanol, and methanol as benchmark compounds with significant spectral overlaps. A measurement precision of 1-10 ppb is obtained after integration for 10 s at amount fractions below 10 ppm, and excellent linearity is found over at least 3 orders of magnitude. Combined with our dedicated spectral fitting algorithm, we demonstrate highly selective multicompound analyses with less than 3.5% relative expanded uncertainty, even in the presence of a 40× excess of an interfering compound with complete spectral overlap.

A High-Precision Mid-Infrared Spectrometer for Ambient HNO3 Measurements.

Precise and accurate measurements of ambient HNO3 are crucial for understanding various atmospheric processes, but its ultra-low trace amounts and the high polarity of HNO3 have strongly hindered routine, widespread, direct measurements of HNO3 and restricted field studies to mostly short-term, localized measurement campaigns. Here, we present a custom field-deployable direct absorption laser spectrometer and demonstrate its analytical capabilities for in situ atmospheric HNO3 measurements. Detailed laboratory characterizations with a particular focus on the instrument response under representative conditions for tropospheric measurements, i.e., the humidity, spectral interference, changing HNO3 amount fractions, and air-sampling-related artifacts, revealed the key aspects of our method: (i) a good linear response (R2 > 0.98) between 0 and 25 nmol·mol−1 in both dry and humid conditions with a limit of detection of 95 pmol·mol−1; (ii) a discrepancy of 20% between the spectroscopically derived amount fractions and indirect measurements using liquid trapping and ion chromatography; (iii) a systematic spectral bias due to water vapor. The spectrometer was deployed in a three-week field measurement campaign to continuously monitor the HNO3 amount fraction in ambient air. The measured values varied between 0.1 ppb and 0.8 ppb and correlated well with the daily total nitrates measured using a filter trapping method.

High-precision ethanol measurement by mid-IR laser absorption spectroscopy for metrological applications.

We report on the development and validation of a compact laser instrument using mid-IR direct absorption spectroscopy (DAS) for high-precision measurements of ethanol in breath-like air mixtures. Leveraging the intermittent continuous wave (iCW) driving for conventional narrow-band distributed feedback (DFB) quantum cascade laser (QCL) emitting around 9.3 µm and using a 25 m path length multiple-pass absorption cell at reduced pressure, a precision of 9 ppb (amount fraction, nmol mol-1) at 60 s integration time is achieved even in the presence of 5% of H2O and CO2. Thus, the instrument is well suitable for metrological studies to investigate observed, but yet unquantified, discrepancies between different breath alcohol reference-generation methods. The approach can be generalized and applied for other organic molecules in a wide range of applications.

Laser driving and data processing concept for mobile trace gas sensing: Design and implementation.

High precision mobile sensing of multi-species gases is greatly demanded in a wide range of applications. Although quantum cascade laser absorption spectroscopy demonstrates excellent field-deployment capabilities for gas sensing, the implementation of this measurement technique into sensor-like portable instrumentation still remains challenging. In this paper, two crucial elements, the laser driving and data acquisition electronics, are addressed. Therefore, we exploit the benefits of the time-division multiplexed intermittent continuous wave driving concept and the real-time signal pre-processing capabilities of a commercial System-on-Chip (SoC, Red Pitaya). We describe a re-designed current driver that offers a universal solution for operating a wide range of multi-wavelength quantum cascade laser device types and allows stacking for the purpose of multiple laser configurations. Its adaptation to the various driving situations is enabled by numerous field programmable gate array (FPGA) functionalities that were developed on the SoC, such as flexible generation of a large variety of synchronized trigger signals and digital inputs/outputs (DIOs). The same SoC is used to sample the spectroscopic signal at rates up to 125 MS/s with 14-bit resolution. Additional FPGA functionalities were implemented to enable on-board averaging of consecutive spectral scans in real-time, resulting in optimized memory bandwidth and hardware resource utilisation and autonomous system operation. Thus, we demonstrate how a cost-effective, compact, and commercial SoC can successfully be adapted to obtain a fully operational research-grade laser spectrometer. The overall system performance was examined in a spectroscopic setup by analyzing low pressure absorption features of CO2 at 4.3 µm.