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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.

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

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.

New results obtained in the development of quartz-enhanced photoacoustic gas sensors are reported. This will include recent advances provided by the implementation of the 2nd generation and 3rd generation of custom QTFs.

PREP spectroscopy on OH- in H-bonded liquids reveals an ultrafast geminate recombination channel. The process is assigned to formation of short-lieved OH:e- pairs facilitated by the inhomogeneous local H-bonding environment of OH-.

Photolysis of liquid water produces free OH radicals, hydronium ions and electrons. Initially, free electrons in solution are trapped rapidly and the partially and fully solvated electrons have the potential for further reactions [1]. It is suspected that they are involved in a number of still poorly understood dissociative electro-nattachment processes in radiation biology. The ionization mechanism of water is significant for the relative spatial distributions of the nascent species that ultimately govern their subsequent chemistry [2].

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.

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.

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 &mu, m capable of targeting a CH4 absorption line at 2988.8 cm&minus, 1 and a water line at 2988.6 cm&minus, 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.