A pre-Campanian Ignimbrite techno-cultural shift in the Aurignacian sequence of Grotta di Castelcivita, southern Italy.

The Aurignacian is the first European technocomplex assigned to Homo sapiens recognized across a wide geographic extent. Although archaeologists have identified marked chrono-cultural shifts within the Aurignacian mostly by examining the techno-typological variations of stone and osseous tools, unraveling the underlying processes driving these changes remains a significant scientific challenge. Scholars have, for instance, hypothesized that the Campanian Ignimbrite (CI) super-eruption and the climatic deterioration associated with the onset of Heinrich Event 4 had a substantial impact on European foraging groups. The technological shift from the Protoaurignacian to the Early Aurignacian is regarded as an archaeological manifestation of adaptation to changing environments. However, some of the most crucial regions and stratigraphic sequences for testing these scenarios have been overlooked. In this study, we delve into the high-resolution stratigraphic sequence of Grotta di Castelcivita in southern Italy. Here, the Uluzzian is followed by three Aurignacian layers, sealed by the eruptive units of the CI. Employing a comprehensive range of quantitative methods-encompassing attribute analysis, 3D model analysis, and geometric morphometrics-we demonstrate that the key technological feature commonly associated with the Early Aurignacian developed well before the deposition of the CI tephra. Our study provides thus the first direct evidence that the volcanic super-eruption played no role in this cultural process. Furthermore, we show that local paleo-environmental proxies do not correlate with the identified patterns of cultural continuity and discontinuity. Consequently, we propose alternative research paths to explore the role of demography and regional trajectories in the development of the Upper Paleolithic.

Ultra-highly sensitive dual gases detection based on photoacoustic spectroscopy by exploiting a long-wave, high-power, wide-tunable, single-longitudinal-mode solid-state laser.

Photoacoustic spectroscopy (PAS) as a highly sensitive and selective trace gas detection technique has extremely broad application in many fields. However, the laser sources currently used in PAS limit the sensing performance. Compared to diode laser and quantum cascade laser, the solid-state laser has the merits of high optical power, excellent beam quality, and wide tuning range. Here we present a long-wave, high-power, wide-tunable, single-longitudinal-mode solid-state laser used as light source in a PAS sensor for trace gas detection. The self-built solid-state laser had an emission wavelength of ~2 µm with Tm:YAP crystal as the gain material, with an excellent wavelength and optical power stability as well as a high beam quality. The wide wavelength tuning range of 9.44 nm covers the absorption spectra of water and ammonia, with a maximum optical power of ~130 mW, allowing dual gas detection with a single laser source. The solid-state laser was used as light source in three different photoacoustic detection techniques: standard PAS with microphone, and external- and intra-cavity quartz-enhanced photoacoustic spectroscopy (QEPAS), proving that solid-state laser is an attractive excitation source in photoacoustic spectroscopy.

Quartz-enhanced multiheterodyne resonant photoacoustic spectroscopy.

The extension of dual-comb spectroscopy (DCS) to all wavelengths of light along with its ability to provide ultra-large dynamic range and ultra-high spectral resolution, renders it extremely useful for a diverse array of applications in physics, chemistry, atmospheric science, space science, as well as medical applications. In this work, we report on an innovative technique of quartz-enhanced multiheterodyne resonant photoacoustic spectroscopy (QEMR-PAS), in which the beat frequency response from a dual comb is frequency down-converted into the audio frequency domain. In this way, gas molecules act as an optical-acoustic converter through the photoacoustic effect, generating heterodyne sound waves. Unlike conventional DCS, where the light wave is detected by a wavelength-dependent photoreceiver, QEMR-PAS employs a quartz tuning fork (QTF) as a high-Q sound transducer and works in conjunction with a phase-sensitive detector to extract the resonant sound component from the multiple heterodyne acoustic tones, resulting in a straightforward and low-cost hardware configuration. This novel QEMR-PAS technique enables wavelength-independent DCS detection for gas sensing, providing an unprecedented dynamic range of 63 dB, a remarkable spectral resolution of 43 MHz (or ~0.3 pm), and a prominent noise equivalent absorption of 5.99 × 10-6 cm-1·Hz-1/2.

Carbon monoxide impurities in hydrogen detected with resonant photoacoustic cell using a mid-IR laser source.

We report on a photoacoustic sensor system based on a differential photoacoustic cell to detect the concentration of CO impurities in hydrogen. A DFB-QCL laser with a central wavelength of 4.61 µm was employed as an exciting source with an optical power of 21 mW. Different concentrations of CO gas mixed with pure hydrogen were injected into the photoacoustic cell to test the linear response of the photoacoustic signal to the CO concentration. The stability of the long-term operation was verified by Allan-Werle deviation analysis. The minimum detection limit (MDL, SNR=1) results 8 ppb at 1 s and reaches a sub-ppb level at 100 s of integration time. Dynamic response of the system is linear and has been tested up to the concentration of 6 ppm. Saturation conditions are expected to be reached for CO concentration larger than 100 ppm.

Folded-optics-based quartz-enhanced photoacoustic and photothermal hybrid spectroscopy.

Folded-optics-based quartz-enhanced photoacoustic and photothermal hybrid spectroscopy (FO-QEPA-PTS) is reported for the first time. In FO-QEPA-PTS, the detection of the photoacoustic and photothermal hybrid signal is achieved through the use of a custom quartz tuning fork (QTF), thereby mitigating the issue of resonant frequency mismatch typically encountered in quartz-enhanced photoacoustic-photothermal spectroscopy employing multiple QTFs. A multi-laser beam, created by a multi-pass cell (MPC) with a designed single-line spot pattern, partially strikes the inner edge of the QTF and partially passes through the prong of the QTF, thereby generating photoacoustic and photothermal hybrid signals. To assess the performance of FO-QEPA-PTS, 1 % acetylene is selected as the analyte gas and the 2f signals produced by the photoacoustic, the photothermal, and their hybrid effects are measured. Comparative analysis against QEPAS and QEPTS reveals signal gain factors of ∼ 79 and ∼ 14, respectively, when these laser beams created by MPC excite the QTF operating at fundamental resonance mode in phase. In the FO-QEPA-PTS signal, the proportions of the photoacoustic and the photothermal effects induced by the multiple beams are ∼7 % and 93 %, respectively.

End-to-end methane gas detection algorithm based on transformer and multi-layer perceptron.

In this paper, an end-to-end methane gas detection algorithm based on transformer and multi-layer perceptron (MLP) for tunable diode laser absorption spectroscopy (TDLAS) is presented. It consists of a Transformer-based U-shaped Neural Network (TUNN) filtering algorithm and a concentration prediction network (CPN) based on MLP. This algorithm employs an end-to-end architectural design to extract information from noisy transmission spectra of methane and derive the CH4 concentrations from denoised spectra, without intermediate steps. The results demonstrate the superiority of the proposed TUNN filtering algorithm over other typically employed digital filters. For concentration prediction, the determination coefficient (R2) reached 99.7%. Even at low concentrations, R2 remained notably high, reaching up to 89%. The proposed algorithm results in a more efficient, convenient, and accurate spectral data processing for TDLAS-based gas sensors.

Lithium Niobate - Enhanced Photoacoustic Spectroscopy.

In this work, we report on the novel employment of lithium niobate tuning forks as acoustic transducers in photoacoustic spectroscopy for gas sensing. The lithium niobate tuning fork (LiNTF) exhibits a fundamental resonance frequency of 39196.6 Hz and a quality factor Q = 5900 at atmospheric pressure. The possibility to operate the LiNTF as a photoacoustic wave detector was demonstrated targeting a water vapor absorption line falling at 7181.14 cm-1 (1.39 µm). A noise equivalent concentration of 2 ppm was reached with a signal integration time of 20 s. These preliminary results open the path towards integrated photonic devices for gas sensing with LiNTF-based detectors on lithium niobate platforms.

Influence of climate change on wastewater treatment plants performances and energy costs in Apulia, south Italy.

This paper studies the influence of temperature and of rainfall intensity and the effect of such variations on the treatment efficiencies and on the electrical consumptions in seven medium-large size Wastewater Treatment Plants (WWTPs) in Apulia in South Italy (Bari, Barletta, Brindisi, Lecce, Foggia, Andria and Taranto). It has been observed, in the considered WWTPs, a slight but clear increase of the incoming flow due to the increase in rainfall intensity, which results to an increase of the energy consumption per incoming volume. The impact of the climate change to the incoming flow, during the last five years (2016-2020), has been assessed indicating that an increase in rainfall intensity results to an increase of the WWTPs energy consumptions per wastewater treated volume. More specifically, for a specific WWTP (Lecce) it was found that the electrical consumption increases from 0.36 kw/m3 to 0.51 kw/m3 when the rainfall intensity was increased from 0.8 mm/min to 2.9 mm/min. Some adaption measures have been considered to upgrade the existing WWTP so to mitigate the energy increase and to limit the global effects of climate change.

Ppb-level NH3 photoacoustic sensor combining a hammer-shaped tuning fork and a 9.55 µm quantum cascade laser.

We present a quartz enhanced photoacoustic spectroscopy (QEPAS) gas sensor designed for precise monitoring of ammonia (NH3) at ppb-level concentrations. The sensor is based on a novel custom quartz tuning fork (QTF) with a mid-infrared quantum cascade laser emitting at 9.55 µm. The custom QTF with a hammer-shaped prong geometry which is also modified by surface grooves is designed as the acoustic transducer, providing a low resonance frequency of 9.5 kHz and a high-quality factor of 10263 at atmospheric pressure. In addition, a temperature of 50 °C and a large gas flow rate of 260 standard cubic centimeters per minute (sccm) are applied to mitigate the adsorption and desorption effect arising from the polarized molecular of NH3. With 80-mW optical power and 300-ms lock-in integration time, the detection limit is achieved to be 2.2 ppb which is the best value reported in the literature so far for NH3 QEPAS sensors, corresponding to a normalized noise equivalent absorption coefficient of 1.4 × 10-8 W cm-1 Hz-1/2. A five-day continuous monitoring for atmospheric NH3 is performed, verifying the stability and robustness of the presented QEPAS-based NH3 sensor.

Light-induced thermoelastic sensor for ppb-level H2S detection in a SF6 gas matrices exploiting a mini-multi-pass cell and quartz tuning fork photodetector.

We present an optical sensor based on light-induced thermoelastic spectroscopy for the detection of hydrogen sulfide (H2S) in sulfur hexafluoride (SF6). The sensor incorporates a compact multi-pass cell measuring 6 cm × 4 cm × 4 cm and utilizes a quartz tuning fork (QTF) photodetector. A 1.58 µm near-infrared distributed feedback (DFB) laser with an optical power of 30 mW serves as the excitation source. The sensor achieved a minimum detection limit (MDL) of ∼300 ppb at an integration time of 300 ms, corresponding to a normalized noise equivalent absorption coefficient (NNEA) of 3.96 × 10-9 W·cm-1·Hz-1/2. By extending the integration time to 100 s, the MDL can be reduced to ∼25 ppb. The sensor exhibits a response time of ∼1 min for a gas flow rate of 70 sccm.

Quartz-Enhanced Photoacoustic Sensor Based on a Multi-Laser Source for In-Sequence Detection of NO2, SO2, and NH3.

In this work, we report on the implementation of a multi-quantum cascade laser (QCL) module as an innovative light source for quartz-enhanced photoacoustic spectroscopy (QEPAS) sensing. The source is composed of three different QCLs coupled with a dichroitic beam combiner module that provides an overlapping collimated beam output for all three QCLs. The 3λ-QCL QEPAS sensor was tested for detection of NO2, SO2, and NH3 in sequence in a laboratory environment. Sensitivities of 19.99 mV/ppm, 19.39 mV/ppm, and 73.99 mV/ppm were reached for NO2, SO2, and NH3 gas detection, respectively, with ultimate detection limits of 9 ppb, 9.3 ppb, and 2.4 ppb for these three gases, respectively, at an integration time of 100 ms. The detection limits were well below the values of typical natural abundance of NO2, SO2, and NH3 in air.

Assessment of vibrational-translational relaxation dynamics of in a wet-nitrogen matrix through QEPAS.

Here we report on a study of the non-radiative relaxation dynamic of 12CH4 and 13CH4 in wet nitrogen-based matrixes by using the quartz-enhanced photoacoustic spectroscopy (QEPAS) technique. The dependence of the QEPAS signal on pressure at fixed matrix composition and on H2O concentration at fixed pressure was investigated. We demonstrated that QEPAS measurements can be used to retrieve both the effective relaxation rate in the matrix, and the V-T relaxation rate associated to collisions with nitrogen and water vapor. No significant differences in measured relaxation rates were observed between the two isotopologues.

Quartz-enhanced photoacoustic spectroscopy (QEPAS) and Beat Frequency-QEPAS techniques for air pollutants detection: A comparison in terms of sensitivity and acquisition time.

In this work, a comparison between Quartz Enhanced Photoacoustic Spectroscopy (QEPAS) and Beat Frequency-QEPAS (BF-QEPAS) techniques for environmental monitoring of pollutants is reported. A spectrophone composed of a T-shaped Quartz Tuning Fork (QTF) coupled with resonator tubes was employed as a detection module. An interband cascade laser has been used as an exciting source, allowing the targeting of two NO absorption features, located at 1900.07 cm-1 and 1900.52 cm-1, and a water vapor absorption feature, located at 1901.76 cm-1. Minimum detection limits of 90 ppb and 180 ppb were achieved with QEPAS and BF-QEPAS techniques, respectively, for NO detection. The capability to detect multiple components in the same gas mixture using BF-QEPAS was also demonstrated.

Signal-to-Noise Ratio Analysis for the Voltage-Mode Read-Out of Quartz Tuning Forks in QEPAS Applications.

Quartz tuning forks (QTFs) are employed as sensitive elements for gas sensing applications implementing quartz-enhanced photoacoustic spectroscopy. Therefore, proper design of the QTF read-out electronics is required to optimize the signal-to-noise ratio (SNR), and in turn, the minimum detection limit of the gas concentration. In this work, we present a theoretical study of the SNR trend in a voltage-mode read-out of QTFs, mainly focusing on the effects of (i) the noise contributions of both the QTF-equivalent resistor and the input bias resistor RL of the preamplifier, (ii) the operating frequency, and (iii) the bandwidth (BW) of the lock-in amplifier low-pass filter. A MATLAB model for the main noise contributions was retrieved and then validated by means of SPICE simulations. When the bandwidth of the lock-in filter is sufficiently narrow (BW = 0.5 Hz), the SNR values do not strongly depend on both the operating frequency and RL values. On the other hand, when a wider low-pass filter bandwidth is employed (BW = 5 Hz), a sharp SNR peak close to the QTF parallel-resonant frequency is found for large values of RL (RL > 2 MΩ), whereas for small values of RL (RL < 2 MΩ), the SNR exhibits a peak around the QTF series-resonant frequency.

Commercial and Custom Quartz Tuning Forks for Quartz Enhanced Photoacoustic Spectroscopy: Stability under Humidity Variation.

This work investigates the behavior of commercial and custom Quartz tuning forkss (QTF) under humidity variations. The QTFs were placed inside a humidity chamber and the parameters were studied with a setup to record the resonance frequency and quality factor by resonance tracking. The variations of these parameters that led to a 1% theoretical error on the Quartz Enhanced Photoacoustic Spectroscopy (QEPAS) signal were defined. At a controlled level of humidity, the commercial and custom QTFs present similar results. Therefore, commercial QTFs appear to be a very good candidates for QEPAS as they are also affordable and small. When the humidity increases from 30 to 90 %RH, the variations in the custom QTFs' parameters remain suitable, while commercial QTFs show unpredictable behavior.

Evaluation of greenhouse gas emissions from aerobic and anaerobic wastewater treatment plants in Southeast of Italy.

An evaluation of the operative functioning data of 183 Wastewater Treatment Plants (WWTPs) in Apulia (Southeast of Italy) has been carried out aimed to assess their Green House Gases (GHGs) emissions and the level for which the use of anaerobic sludge treatment should be more convenient in terms of electricity consumption and of GHGs emissions. Out of the 183 studies WWTPs, 140 are practicing aerobic digestion of sludge, while the remaining 43 are practicing anaerobic digestion of sludge. WWTPs in Apulia are serving about 4,81 million PE (Population Equivalent), yielding approximately 600,000-ton equivalent CO2 per annum. The production of GHGs emissions has been estimated by evaluating the contribution of CO2 deriving from: a) electric energy consumption (fossil CO2), b) biogenic CO2, c) N2O and d) CH4 emissions. The present study investigates a number of technical measures for upgrading the existing WWTPs, so to reduce GHGs emissions through the amelioration of CH4 production and capture in the anaerobic step, and through reducing the production of biogenic N2O and CO2 emissions in the aerated basin. The methodology employees artificial intelligence-based control for upgrading the aerobic oxidation of the organic carbon and the nitrification-denitrification steps. As a result, GHGs emissions are expected to be reduced by approximately: 71% for CH4, 57% for N2O, 20% for biogenic CO2 and 15% for fossil derived CO2.

Side-excitation light-induced thermoelastic spectroscopy.

In this Letter, a side-excitation light-induced thermoelastic spectroscopy (SE-LITES) technique was developed for trace gas detection. A novel, to the best of our knowledge, custom quartz tuning fork (QTF) was used as a transducer for photon detection by the thermoelastic effect. The mechanical stress distribution on the QTF surface was analyzed to identify the optimum thermoelastic excitation approach. The electrode film on the QTF surface also works as a partially reflective layer to obtain a long optical absorption path inside the QTF body. With the long optical absorption length and the inner face excitation of the QTF, the thermoelastic effect was greatly enhanced. With an optimized modulation depth, a signal-to-noise ratio (SNR) improvement of more than one order of magnitude was achieved, compared to traditional LITES.

Methane and ethane detection from natural gas level down to trace concentrations using a compact mid-IR LITES sensor based on univariate calibration.

A gas sensor based on light-induced thermo-elastic spectroscopy (LITES) capable to detect methane (C1) and ethane (C2) in a wide concentration range, from percent down to part-per-billion (ppb), is here reported. A novel approach has been implemented, exploiting a compact sensor design that accommodates both a custom 9.8 kHz quartz tuning fork (QTF) used as photodetector and the gas sample in the same housing. The resulting optical pathlength was only 2.5 cm. An interband cascade laser (ICL) with emission wavelength of 3.345 µm was used to target absorption features of C1 and C2. The effects of high concentration analytes on sensor response were firstly investigated. C1 concentration varied from 1% to 10%, while C2 concentration varied from 0.1% to 1%. These ranges were selected to retrace the typical natural gas composition in a 1:10 nitrogen dilution. The LITES sensor was calibrated for both the gas species independently and returned nonlinear but monotonic responses for the two analytes. These univariate calibrations were used to retrieve the composition of C1-C2 binary mixtures with accuracy higher than 98%, without the need for further data analysis. Minimum detection limits of ∼650 ppb and ∼90 ppb were achieved at 10 s of integration time for C1 and C2, respectively, demonstrating the capability of the developed LITES sensor to operate with concentration ranges spanning over 6 orders of magnitude.