Environmental Monitoring of Methane with Quartz-Enhanced Photoacoustic Spectroscopy Exploiting an Electronic Hygrometer to Compensate the H2O Influence on the Sensor Signal.

A dual-gas sensor based on the combination of a quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor and an electronic hygrometer was realized for the simultaneous detection of methane (CH4) and water vapor (H2O) in air. The QEPAS sensor employed an interband cascade laser operating at 3.34 µm capable of targeting a CH4 absorption line at 2988.8 cm-1 and a water line at 2988.6 cm-1. Water vapor was measured with both the electronic hygrometer and the QEPAS sensor for comparison. The measurement accuracy provided by the hygrometer enabled the adjustment of methane QEPAS signal with respect to the water vapor concentration to retrieve the actual CH4 concentration. The sensor was tested by performing prolonged measurements of CH4 and H2O over 60 h to demonstrate the effectiveness of this approach for environmental monitoring applications.

Dual-Gas Quartz-Enhanced Photoacoustic Sensor for Simultaneous Detection of Methane/Nitrous Oxide and Water Vapor.

The development of a dual-gas quartz-enhanced photoacoustic (QEPAS) sensor capable of simultaneous detection of water vapor and alternatively methane or nitrous oxide is reported. A diode laser and a quantum cascade laser (QCL) excited independently and simultaneously both the fundamental and the first overtone flexural mode of the quartz tuning fork (QTF), respectively. The diode laser targeted a water absorption line located at 7181.16 cm-1 (1.392 µm), while the QCL emission wavelength is centered at 7.71 µm and was tuned to target two strong absorption lines of methane and nitrous oxide, located at 1297.47 and 1297.05 cm-1, respectively. Two sets of microresonator tubes were positioned, respectively, at the antinode points of the fundamental and the first overtone flexural modes of the QTF to enhance the QEPAS signal-to-noise ratio. Detection limits of 18 ppb for methane, 5 ppb for nitrous oxide and 20 ppm for water vapor have been achieved at a lock-in integration time of 100 ms.

Tuning forks with optimized geometries for quartz-enhanced photoacoustic spectroscopy.

We report on the design, realization, and performance of novel quartz tuning forks (QTFs) optimized for quartz-enhanced photoacoustic spectroscopy (QEPAS). Starting from a QTF geometry designed to provide a fundamental flexural in-plane vibrational mode resonance frequency of ~16 kHz, with a quality factor of 15,000 at atmospheric pressure, two novel geometries have been realized: a QTF with T-shaped prongs and a QTF with prongs having rectangular grooves carved on both surface sides. The QTF with grooves showed the lowest electrical resistance, while the T-shaped prongs QTF provided the best photoacoustic response in terms of signal-to-noise ratio (SNR). When acoustically coupled with a pair of micro-resonator tubes, the T-shaped QTF provides a SNR enhancement of a factor of 60 with respect to the bare QTF, which represents a record value for mid-infrared QEPAS sensing.

Quartz-enhanced photoacoustic sensor for ethylene detection implementing optimized custom tuning fork-based spectrophone.

The design and realization of two highly sensitive and easily interchangeable spectrophones based on custom quartz tuning forks, with a rectangular (S1) or T-shaped (S2) prongs geometry, is reported. The two spectrophones have been implemented in a QEPAS sensor for ethylene detection, employing a DFB-QCL emitting at 10.337 µm with an optical power of 74.2 mW. A comparison between their performances showed a signal-to-noise ratio 3.4 times higher when implementing the S2 spectrophone. For the S2-based sensor, a linear dependence of the QEPAS signal on ethylene concentration was demonstrated in the 5 ppm -100 ppm range. For a 10 s lock-in integration time, an ethylene minimum detection limit of 10 ppb was calculated.

Octupole electrode pattern for tuning forks vibrating at the first overtone mode in quartz-enhanced photoacoustic spectroscopy.

The design, realization, and performance analysis of an octupole electrode pattern configuration intended for the optimization of the charge collection efficiency in quartz tuning forks (QTFs) vibrating at the first overtone in-plane flexural mode is reported. Two QTFs having the same geometry, but differing in the electrode pattern deposited on the QTF prongs, have been realized in order to study the influence of the electrode pattern on the resonance quality factor and electrical resistance. A standard quadrupole pattern (optimized for the fundamental mode) and an octupole electrode layout have been implemented. Although both QTFs show the same resonance quality factor for the first overtone, the octupole pattern provides a reduction of the QTF electrical resistance by more than four times. The sensing performance of the two QTFs has been compared by employing them in a mid-IR quartz-enhanced photoacoustic sensor (QEPAS) system targeting a water absorption line. When operating at the first overtone mode, the QTF with an octupole electrode pattern provides a QEPAS signal more than two times higher with respect to the QTF employing the standard quadrupole configuration.

Compact and portable quartz-enhanced photoacoustic spectroscopy sensor for carbon monoxide environmental monitoring in urban areas.

We report on the realization, calibration, and test outdoor of a 19-inches rack 3-units sized Quartz Enhanced Photoacoustic Spectroscopy (QEPAS) trace gas sensor designed for real-time carbon monoxide monitoring in ambient air. Since CO acts as a slow energy relaxer when excited in the mid-infrared spectral region, its QEPAS signal is affected by the presence of relaxation promoters, such as water vapor, or quenchers like molecular oxygen. We analyzed in detail all the CO relaxation processes with typical collisional partners in an ambient air matrix and used this information to evaluate oxygen and humidity-related effects, allowing the real CO concentration to be retrieved. The sensor was tested outdoor in a trafficked urban area for several hours providing results comparable with the daily averages reported by the local air inspection agency, with spikes in CO concentration correlated to the passages of heavy-duty vehicles.

Novel geminate recombination channel after indirect photoionization of water.

We studied the photolysis of neat protonated and heavy water using pump-probe and pump-repump-probe spectroscopy. A novel recombination channel is reported leading to ultrafast quenching (0.7 ± 0.1 ps) of almost one third of the initial number of photo-generated electrons. The efficiency and the recombination rate of this channel are lower in heavy water, 27 ± 5% and (0.9 ± 0.1 ps)(-1), respectively. Comparison with similar data measured after photodetachment of aqueous hydroxide provides evidence for the formation of short-lived OH:e(-) (OD:e(-)) pairs after indirect photoionization of water at 9.2 eV.

Loss Mechanisms Determining the Quality Factors in Quartz Tuning Forks Vibrating at the Fundamental and First Overtone Modes.

Quartz tuning forks (QTFs) are piezo-transducers that have been implemented for numerous applications, such as chemical gas sensing, atomic force microscopy, rheology, and industrial process control. The most important parameter for QTFs' sensing application is the resonance quality factor (Q-factor). An experimental investigation and theoretical analysis of the influence of QTFs' geometries on the Q-factor of the flexural fundamental and first overtone resonance modes are reported. The resonance frequencies and related Q-factors for five different QTFs have been measured. The QTF response was recorded at different air pressures to investigate the influence of the surrounding medium on the Q-factor. A data analysis demonstrated that air viscous damping is the dominant energy dissipation mechanism for both flexural modes. Thermoelastic and support losses are additional contributions that depend on the QTF geometry. A study of the QTF damping mechanism dependence upon the prong geometry is also provided.

Hydrogen Atom Transfer from Water or Alcohols Activated by Presolvated Electrons.

High-energy irradiation of protic solvents can transiently introduce excess electrons that are implicated in a diverse range of reductive processes. Here we report the evolution of electron solvation in water and in alcohols following photodetachment from aqueous hydroxide or the corresponding alkoxides studied by two- and three-pulse femtosecond spectroscopy and ab initio molecular dynamic simulations. The experiments reveal an ultrafast recombination channel of the excess electrons. Through the calculations this channel emerges as an H-atom transfer process to the hydroxyl or alkoxy radical species from neighboring solvent molecules, which are activated as the presolvated electron occupies their antibonding orbitals. The initially low activation barrier in the early stages of electron solvation was found to increase (from 12 to 44 kJ/mol in water) as full solvation proceeded.