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11 pages, 488 KiB  
Article
A Deep Learning Approach to Investigating Clandestine Laboratories Using a GC-QEPAS Sensor
by Giorgio Felizzato, Nicola Liberatore, Sandro Mengali, Roberto Viola, Vittorio Moriggia and Francesco Saverio Romolo
Chemosensors 2024, 12(8), 152; https://doi.org/10.3390/chemosensors12080152 - 5 Aug 2024
Viewed by 1044
Abstract
Illicit drug production in clandestine laboratories involves the use of large quantities of different chemicals that can be obtained for legitimate purposes. The identification of these chemicals, including reagents, catalyzers and solvents, is crucial for forensic investigations. From a legal point of view, [...] Read more.
Illicit drug production in clandestine laboratories involves the use of large quantities of different chemicals that can be obtained for legitimate purposes. The identification of these chemicals, including reagents, catalyzers and solvents, is crucial for forensic investigations. From a legal point of view, a drug precursor is a material that is specific and critical to the production of a finished chemical and that constitutes a significant portion of the final molecular structure of the drug. In this study, a gas chromatography quartz-enhanced photoacoustic spectroscopy (GC-QEPAS) sensor—in conjunction with a deep learning model—was evaluated for its effectiveness in the detection and identification of interesting compounds for the production of amphetamine, methamphetamine, 3,4-methylenedioxymethamphetamine (MDMA), phenylcyclohexyl piperidine (PCP), and cocaine. The GC-QEPAS sensor includes a gas sampler, a fast GC for separation, and a QEPAS detector, which excites molecules exiting the GC column using a quantum cascade laser to provide the infra-red (IR) spectrum. The on-site capability of the GC-QEPAS system offers significant advantages over the current instruments employed in this field, including rapid analysis, which is crucial in field operations. This allows law enforcement to quickly identify specimens of interest on site. The system’s performance was validated by taking into account the limit of detection, repeatability, and within-laboratory reproducibility. The results showed excellent repeatability and reproducibility for both the GC and QEPAS modules. The deep learning model, a multilayer perceptron neural network, was trained using IR spectra and retention times, achieving very high classification accuracy in the testing conditions. This study demonstrated the efficacy of the GC-QEPAS sensor combined with a deep learning model for the reliable identification of drug precursors, providing a robust tool for law enforcement during criminal investigations in clandestine laboratories. Full article
(This article belongs to the Special Issue Chemical Sensing and Analytical Methods for Forensic Applications)
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<p>Multilayer perceptron scheme.</p>
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15 pages, 1951 KiB  
Article
Insight into the Effects of Norfloxacin on Bacterial Community and Antibiotic Resistance Genes during Chicken Manure Composting
by Yao Feng, Huading Shi, Yang Fei, Quansheng Zhao and Zhaojun Li
Fermentation 2024, 10(7), 366; https://doi.org/10.3390/fermentation10070366 - 18 Jul 2024
Cited by 1 | Viewed by 967
Abstract
Composting emerges as an effective strategy to eliminate antibiotics and antibiotic resistance genes (ARGs) in animal manure. In this study, chicken manure with the addition of wheat straw and sawdust was used as composting raw materials, and different concentrations of norfloxacin were added [...] Read more.
Composting emerges as an effective strategy to eliminate antibiotics and antibiotic resistance genes (ARGs) in animal manure. In this study, chicken manure with the addition of wheat straw and sawdust was used as composting raw materials, and different concentrations of norfloxacin were added to investigate its effects on physicochemical properties, bacterial community, and ARGs during the composting process. Results show that the presence of norfloxacin has obvious effects on the composting physicochemical properties and germination index (GI). A high concentration of norfloxacin influences the succession direction of the bacterial community and promotes the transfers of gyrA, gyrB, parC, qepA, and qnrB. The composting physicochemical properties alter bacterial communities and further influence the fate of ARGs. These results suggest that meticulous management of antibiotic usage and compost conditions are vital strategies for mitigating the influx of antibiotics and ARGs into the environment, both at the source and on the path. Full article
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<p>Dynamic changes in the temperature (<b>a</b>), moisture content (<b>b</b>), pH (<b>c</b>), TOC content (<b>d</b>), TN content (<b>e</b>), and C/N (<b>f</b>) during the composting process. Results are the mean of three replicates; bars indicate the standard error. TOC: total organic carbon; TN: total nitrogen; NOR0: no norfloxacin; NOR0.6: spiked with 0.6 mg kg<sup>−1</sup> of norfloxacin; NOR25: spiked with 25 mg kg<sup>−1</sup> of norfloxacin; NOR50: spiked with 50 mg kg<sup>−1</sup> of norfloxacin; NOR75: spiked with 75 mg kg<sup>−1</sup> of norfloxacin; NOR100: spiked with 100 mg kg<sup>−1</sup> of norfloxacin, similarly hereinafter.</p>
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<p>Dynamic changes in the GI of the compost. Results are the mean of three replicates; bars indicate the standard error.</p>
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<p>The fate of NOR throughout the composting process. Results are the mean of three replicates; bars indicate the standard error.</p>
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<p>Alpha diversity, including Chao1 and Shannon indexes (<b>a</b>) and beta diversity (<b>b</b>), of bacterial communities of different treatments.</p>
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<p>Bacterial community composition at the phylum (<b>a</b>) and genus (<b>b</b>) level during the composting process. NOR0 and NOR100 represent treatments without norfloxacin and with norfloxacin concentrations of 100 mg kg<sup>−1</sup>, respectively. And d1, d3, d7, d14, and d45 represent day 1, day 3, day 7, day 14, and day 45 of composting, respectively.</p>
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<p>The correlation heatmap among composting environmental factors, norfloxacin, bacterial genera, and ARGs. “*,**,***” represents that the correlation is significant at the 0.05, 0.01, and 0.001 level, respectively.</p>
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10 pages, 2115 KiB  
Article
Quartz Enhanced Photoacoustic Spectroscopy on Solid Samples
by Judith Falkhofen, Marc-Simon Bahr, Bernd Baumann and Marcus Wolff
Sensors 2024, 24(13), 4085; https://doi.org/10.3390/s24134085 - 24 Jun 2024
Viewed by 3607
Abstract
Quartz-Enhanced Photoacoustic Spectroscopy (QEPAS) is a technique in which the sound wave is detected by a quartz tuning fork (QTF). It enables particularly high specificity with respect to the excitation frequency and is well known for an extraordinarily sensitive analysis of gaseous samples. [...] Read more.
Quartz-Enhanced Photoacoustic Spectroscopy (QEPAS) is a technique in which the sound wave is detected by a quartz tuning fork (QTF). It enables particularly high specificity with respect to the excitation frequency and is well known for an extraordinarily sensitive analysis of gaseous samples. We have developed the first photoacoustic (PA) cell for QEPAS on solid samples. Periodic heating of the sample is excited by modulated light from an interband cascade laser (ICL) in the infrared region. The cell represents a half-open cylinder that exhibits an acoustical resonance frequency equal to that of the QTF and, therefore, additionally amplifies the PA signal. The antinode of the sound pressure of the first longitudinal overtone can be accessed by the sound detector. A 3D finite element (FE) simulation confirms the optimal dimensions of the new cylindrical cell with the given QTF resonance frequency. An experimental verification is performed with an ultrasound micro-electromechanical system (MEMS) microphone. The presented frequency-dependent QEPAS measurement exhibits a low noise signal with a high-quality factor. The QEPAS-based investigation of three different solid synthetics resulted in a linearly dependent signal with respect to the absorption. Full article
(This article belongs to the Special Issue Photoacoustic Sensing, Imaging, and Communications)
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<p>(<b>a</b>) Sound pressure distribution of the second harmonic longitudinal resonance in the centre plane of a half-open cylinder. (<b>b</b>) 3D sound pressure distribution of the second harmonic longitudinal resonance of a half-open cylinder. Dark blue and dark red corresponds to the pressure anti-nodes (180 degrees out of phase).</p>
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<p>The mounting frame (in the exploded view) for the PA cell and the sample in the version for the QTF (the laser-drilled hole is marked with an arrow).</p>
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<p>Experimental setup.</p>
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<p>Normalised microphone signal of the resonance cell as a function of the modulation frequency of the laser together with a fitted Lorentz profile and the QTF resonance frequency.</p>
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<p>QEPAS signal of a solid sample as a function of the modulation frequency of the laser.</p>
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<p>QEPAS signal for three different solid synthetics as a function of absorbance.</p>
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11 pages, 2064 KiB  
Article
Emergence of Plasmid-Mediated Quinolone Resistance (PMQR) Genes in Campylobacter coli in Tunisia and Detection of New Sequence Type ST13450
by Manel Gharbi, Rihab Tiss, Melek Chaouch, Safa Hamrouni and Abderrazak Maaroufi
Antibiotics 2024, 13(6), 527; https://doi.org/10.3390/antibiotics13060527 - 5 Jun 2024
Cited by 1 | Viewed by 1131
Abstract
The aim of this study is to investigate the occurrence of plasmid mediated quinolone resistance (PMQR) determinants in Campylobacter coli isolates collected from broilers, laying hens and poultry farm environments. One hundred and thirty-nine C. coli isolates were isolated from broilers (n = 41), laying [...] Read more.
The aim of this study is to investigate the occurrence of plasmid mediated quinolone resistance (PMQR) determinants in Campylobacter coli isolates collected from broilers, laying hens and poultry farm environments. One hundred and thirty-nine C. coli isolates were isolated from broilers (n = 41), laying hens (n = 53), eggs (n = 4) and the environment (n = 41) of 23 poultry farms located in northeastern of Tunisia. Antimicrobial susceptibility testing was performed on all isolates according to the recommendation of the European Committee on Antimicrobial Susceptibility Testing guidelines. The detection of PMQR genes: qnrA, qnrB, qnrC, qnrD, qnrS, qepA, and aac(6)-Ib gene was performed using polymerase chain reaction (PCR) and specific primers. aac(6′)-Ib amplicons were further analyzed by digestion with BtsCI to identify the aac(6′)-Ib-cr variant. Mutations in GyrA and the occurrence of RE-CmeABC efflux pump were determined by mismatch amplification mutation assay (MAMA) PCR and PCR, respectively. In addition, eleven isolates were selected to determine their clonal lineage by MLST. The 139 C. coli isolates were resistant to ciprofloxacin, and 86 (61.8%) were resistant to nalidixic acid. High rates of resistance were also observed toward erythromycin (100%), azithromycin (96.4%), tetracycline (100%), chloramphenicol (98.56%), ampicillin (66.1%), amoxicillin-clavulanic acid (55.39%), and kanamycin (57.55%). However, moderate resistance rates were observed for gentamicin (9.35%) and streptomycin (22.3%). All quinolone-resistant isolates harbored the Thr-86-Ile amino acid substitution in GyrA, and the RE-CmeABC efflux pump was detected in 40.28% of isolates. Interestingly, the qnrB, qnrS, qepA, and aac(6′)-Ib-cr were detected in 57.7%, 61.15%, 21.58%, and 10% of isolates, respectively. The eleven isolates studied by MLST belonged to a new sequence type ST13450. This study described for the first time the occurrence of PMQR genes in C. coli isolates in Tunisia and globally. Full article
(This article belongs to the Special Issue Antibiotics Resistance in Animals and the Environment)
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<p>Rates of resistance toward tested antimicrobials in the 139 <span class="html-italic">C. coli</span> isolates.</p>
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<p>Genetic relationships of the <span class="html-italic">C. coli</span> ST13450 lineage detected in this study and <span class="html-italic">C. coli</span> isolates from the world (different STs from each country) in the PubMLST database (data taken in April, 2024). (<b>A</b>): a minimum spanning tree was reconstructed based on the ST from this study and the MLST database. The size of circles is proportional to the number of isolates of the same ST in different countries, and the sources of the isolates are colored as indicated. (<b>B</b>): Distribution of STs according to the countries, the size of nodes indicates the number of isolates with identical ST in the country.</p>
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<p>Genetic relationships of the <span class="html-italic">C. coli</span> ST13450 lineage detected in this study and <span class="html-italic">C. coli</span> isolates from the world (different STs from each country) in the PubMLST database (data taken in April, 2024). (<b>A</b>): a minimum spanning tree was reconstructed based on the ST from this study and the MLST database. The size of circles is proportional to the number of isolates of the same ST in different countries, and the sources of the isolates are colored as indicated. (<b>B</b>): Distribution of STs according to the countries, the size of nodes indicates the number of isolates with identical ST in the country.</p>
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<p>Phylogenetic tree based on MLST sequences and allelic profiles of <span class="html-italic">C. coli</span>. Isolates of undetermined STs with allelic profiles deposed in PubMLST database were also included.</p>
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<p>Minimum Spanning Tree of the ST data from <span class="html-italic">C. coli</span> sourced from PubMLST (Different STs from each country). Circle diameter is proportional to the number of isolates of the same ST in different sample sources in the PubMLST database and color depicts sources as indicated in the legend.</p>
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17 pages, 5223 KiB  
Article
Influence of the Gain–Bandwidth of the Front-End Amplifier on the Performance of a QEPAS Sensor
by Luigi Lombardi, Gianvito Matarrese and Cristoforo Marzocca
Acoustics 2024, 6(1), 240-256; https://doi.org/10.3390/acoustics6010013 - 6 Mar 2024
Viewed by 1701
Abstract
The quartz tuning fork used as an acoustic sensor in quartz-enhanced photo-acoustic spectroscopy gas detection systems is usually read out by means of a transimpedance preamplifier based on a low-noise operational amplifier closed in a feedback loop. The gain–bandwidth product of the operational [...] Read more.
The quartz tuning fork used as an acoustic sensor in quartz-enhanced photo-acoustic spectroscopy gas detection systems is usually read out by means of a transimpedance preamplifier based on a low-noise operational amplifier closed in a feedback loop. The gain–bandwidth product of the operational amplifier used in the circuit is a key parameter which must be properly chosen to guarantee that the circuit works as expected. Here, we demonstrate that if the value of this parameter is not sufficiently large, the response of the preamplifier exhibits a peak at a frequency which does not coincide with the series resonant frequency of the quartz tuning fork. If this peak frequency is selected for modulating the laser bias current and is also used as the reference frequency of the lock-in amplifier, a penalty results in terms of signal-to-noise ratio at the output of the QEPAS sensor. This worsens the performance of the gas sensing system in terms of ultimate detection limits. We show that this happens when the front-end preamplifier of the quartz tuning fork is based on some amplifier models that are typically used for such application, both when the integration time of the lock-in amplifier filter is long, to boost noise rejection, and when it is short, in order to comply with a relevant measurement rate. Full article
(This article belongs to the Special Issue Resonators in Acoustics (2nd Edition))
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<p>Simplified block diagram of a QEPAS sensor.</p>
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<p>QTF coupled to micro-resonator tubes.</p>
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<p>QTF read-out by means of a transimpedance preamplifier.</p>
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<p>Butterworth–Van Dyke model of the QTF coupled to the TIA.</p>
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<p>SPICE simulation of the loop gain of the TIA in <a href="#acoustics-06-00013-f003" class="html-fig">Figure 3</a> with the OPAMP OP27.</p>
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<p>Detail of the frequency behavior of |T(jω)| around the resonant frequency of the QTF, for the TIA based on the OP27 OPAMP.</p>
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<p>Equivalent circuit of the TIA after the application of Miller’s theorem to the feedback impedance.</p>
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<p>Simplified circuit for the evaluation of the resonant frequencies of the circuit in <a href="#acoustics-06-00013-f007" class="html-fig">Figure 7</a>.</p>
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<p>Frequency response of the TIA realized with three different OPAMPs.</p>
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<p>Main noise sources in the TIA.</p>
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<p>TIA realized with the AD8067: modulus of the transfer function |H(jω)| obtained with SPICE simulations and Equation (2).</p>
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<p>TIA realized with the AD8067: total output noise power density obtained with SPICE simulations and Equation (12).</p>
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<p>Increasing the loop gain of the TIA based on the OP27 by inserting an ideal voltage amplifier in the feedback loop.</p>
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<p>Comparison between the output noise power spectral densities of the TIA realized with the OP27 and with the same OPAMP, but with loop gain increased by a factor of 20 by means of an ideal voltage amplifier inserted into the feedback loop.</p>
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<p>Comparison between the modulus of the transfer function H<sub>f</sub>(jω) of the TIA realized with the OP27 and with the same OPAMP, but with loop gain increased by a factor of 20.</p>
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<p>SNR at the LIA output as a function of the LIA reference frequency: LIA filter bandwidth BW = 0.1 Hz, TIA realized with the OP27 and with the same OPAMP, but with loop gain increased by a factor of 20.</p>
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<p>SNR at the LIA output as a function of the LIA reference frequency: LIA filter bandwidth BW=3 Hz, TIA achieved with OP27 and with the same OPAMP but with loop gain increased by a factor of 20.</p>
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1195 KiB  
Proceeding Paper
New Photoacoustic Cell Design for Solid Samples
by Judith Falkhofen, Bernd Baumann and Marcus Wolff
Eng. Proc. 2023, 58(1), 86; https://doi.org/10.3390/ecsa-10-16198 - 15 Nov 2023
Cited by 1 | Viewed by 550
Abstract
We have developed a new design for a photoacoustic (PA) cell particularly suited for quartz-enhanced photoacoustic spectroscopy (QEPAS), where a quartz tuning fork (QTF) is used as a sound detector for the PA signal. The cell is designed for the investigation of solid [...] Read more.
We have developed a new design for a photoacoustic (PA) cell particularly suited for quartz-enhanced photoacoustic spectroscopy (QEPAS), where a quartz tuning fork (QTF) is used as a sound detector for the PA signal. The cell is designed for the investigation of solid and semi-solid samples and represents a unilateral open cylinder. The antinode of the sound pressure of the fundamental longitudinal mode of the half-open cylinder occurs directly at the sample, where a measurement is difficult. Therefore, the first harmonic is used. A small hole in the resonator wall at the location of the pressure antinode allows signal detection outside the cylinder without (or only minimally) changing the resonance conditions. This design is particularly simple and easy to manufacture. A finite element (FE) simulation is applied to determine the optimal cell length for the given frequency and the location of the pressure maximum. One difficulty is that the open end dramatically changes the acoustic sound field. We answer the following research questions: where is the sound pressure maximum located and do simple analytical equations agree with the results of the FE simulation? Full article
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<p>Sound pressure distribution of the first harmonic longitudinal resonance of a half-open cylinder.</p>
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<p>Cell with hole (marked with arrow) in a QEPAS off-beam configuration.</p>
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<p>(<b>a</b>) Sound pressure distribution at the central plane of the new cell at <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>f</mi> </mrow> <mrow> <mn>1</mn> </mrow> </msub> <mo>=</mo> <mn>32.768</mn> </mrow> </semantics></math> kHz. Dark blue and dark red correspond to the highest pressure values, which are 180 degrees out of phase. The distance of the maximum sound pressure to the open end is marked. (<b>b</b>) FE mesh. The PML is defined on the outer semi annulus.</p>
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12 pages, 5944 KiB  
Article
Quartz-Enhanced Photoacoustic Sensor Based on a Multi-Laser Source for In-Sequence Detection of NO2, SO2, and NH3
by Pietro Patimisco, Nicoletta Ardito, Edoardo De Toma, Dominik Burghart, Vladislav Tigaev, Mikhail A. Belkin and Vincenzo Spagnolo
Sensors 2023, 23(21), 9005; https://doi.org/10.3390/s23219005 - 6 Nov 2023
Cited by 4 | Viewed by 1302
Abstract
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Photonics for Advanced Spectroscopy and Sensing)
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<p>(<b>a</b>) Schematic of the internal structure of the 3λ-QCL module. F2 is a band-pass filter; F1 is a low-pass filter; M1 is a mirror. (<b>b</b>) Top view of the Solidworks 3D model of the 3λ-QCL module without the top and lateral sides.</p>
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<p>(<b>a</b>) Combined 7.38 μm and 9.06 μm beam profiles overlapped at 25 cm from the 3λ-QCL module. (<b>b</b>) Combined 7.38 μm and 6.25 μm beam profiles overlapped at 25 cm from the 3λ-QCL module.</p>
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<p>(<b>a</b>) Combined 7.38 μm and 9.06 μm beam profiles overlapped at the focal plane of the lens. (<b>b</b>) Combined 7.38 μm and 6.25 μm beam profiles overlapped at the focal plane of the lens. (<b>c</b>) Representation of the three beam spots as circumferences. The 7.41 µm, 6.25 µm, and 9.06 µm beam waists are depicted as green, blue, and red solid circumferences, respectively. The radii of the circumferences are equal to the mean value of widths of the beam waists along the x- and y-directions. The coordinates of the center of the circumferences are those of the peak values of the three beam spots.</p>
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<p>Schematic of the 3λ-QCL-based QEPAS sensor for NH<sub>3</sub>, SO<sub>2</sub>, and NO<sub>2</sub> detection. L—lens; ADM—acoustic detection module; DAQ—data acquisition board; PC—personal computer; PM—power meter.</p>
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<p>(<b>a</b>) HITRAN simulation of an absorption cross-section of a mixture of 10 ppm of NH<sub>3</sub> in N<sub>2</sub>, a mixture of 10 ppm of SO<sub>2</sub> in N<sub>2</sub>, a mixture of 10 ppm of NO<sub>2</sub> in N<sub>2</sub>, and a mixture of 1% of water vapor in standard air within the emission spectral range of the 9.06 μm QCL. (<b>b</b>) Simulation of an absorption cross-section of a mixture of 10 ppm of NO<sub>2</sub> in N<sub>2</sub>, a mixture of 10 ppm of SO<sub>2</sub> in N<sub>2</sub>, a mixture of 10 ppm of NH<sub>3</sub> in N<sub>2</sub>, and a mixture of 1% of water vapor in N<sub>2</sub> within the emission spectral range of the 6.25 μm QCL. (<b>c</b>) Simulation of an absorption cross-section of a mixture of 10 ppm of SO<sub>2</sub> in N<sub>2</sub>, a mixture of 10 ppm of NH<sub>3</sub> in N<sub>2</sub>, a mixture of 10 ppm of NO<sub>2</sub> in N<sub>2</sub>, and a mixture of 1% of water vapor in N<sub>2</sub> within the emission spectral range of the 7.38 μm QCL.</p>
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<p>(<b>a</b>) QEPAS spectral scans measured for different concentrations of NH<sub>3</sub> in N<sub>2</sub> and pure N<sub>2</sub> using the 9.06 μm QCL. (<b>b</b>) QEPAS spectral scans measured for different concentrations of NO<sub>2</sub> in N<sub>2</sub> and pure N<sub>2</sub> obtained when the 6.25 μm QCL is turned on. (<b>c</b>) QEPAS spectral scans measured for different concentrations of SO<sub>2</sub> in N<sub>2</sub> and pure N<sub>2</sub> using the 7.38 μm QCL The peak at 275 mA observed for pure N<sub>2</sub> is due to residual H<sub>2</sub>O in the gas line.</p>
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<p>(<b>a</b>) QEPAS signal as a function of the NH<sub>3</sub> concentration (black squares) with the corresponding best linear fit (red line). (<b>b</b>) QEPAS signal as a function of the NO<sub>2</sub> concentration (black squares) with the corresponding best linear fit (red line). (<b>c</b>) QEPAS signal as a function of the SO<sub>2</sub> concentration (black squares) with the corresponding best linear fit (red line).</p>
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<p>Allan deviation of the QEPAS signal as a function of the lock-in integration time.</p>
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<p>QEPAS spectral scan of NH<sub>3</sub> (<b>a</b>), NO<sub>2</sub> (<b>b</b>), and SO<sub>2</sub> (<b>c</b>) in Mix #1 NO<sub>2</sub>; NH<sub>3</sub> (<b>d</b>), NO<sub>2</sub> (<b>e</b>), and SO<sub>2</sub> (<b>f</b>) in Mix #2; NH<sub>3</sub> (<b>g</b>), NO<sub>2</sub> (<b>h</b>), and SO<sub>2</sub> (<b>i</b>) in Mix #3. The peak at 275 mA observed for pure N<sub>2</sub> is due to residual H<sub>2</sub>O in the gas line.</p>
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14 pages, 2363 KiB  
Article
Quartz-Enhanced Photoacoustic Spectroscopy Assisted by Partial Least-Squares Regression for Multi-Gas Measurements
by Andreas N. Rasmussen, Benjamin L. Thomsen, Jesper B. Christensen, Jan C. Petersen and Mikael Lassen
Sensors 2023, 23(18), 7984; https://doi.org/10.3390/s23187984 - 20 Sep 2023
Viewed by 1235
Abstract
We report on the use of quartz-enhanced photoacoustic spectroscopy (QEPAS) for multi-gas detection. Photoacoustic (PA) spectra of mixtures of water (H2O), ammonia (NH3), and methane (CH4) were measured in the mid-infrared (MIR) wavelength range using a mid-infrared [...] Read more.
We report on the use of quartz-enhanced photoacoustic spectroscopy (QEPAS) for multi-gas detection. Photoacoustic (PA) spectra of mixtures of water (H2O), ammonia (NH3), and methane (CH4) were measured in the mid-infrared (MIR) wavelength range using a mid-infrared (MIR) optical parametric oscillator (OPO) light source. Highly overlapping absorption spectra are a common challenge for gas spectroscopy. To mitigate this, we used a partial least-squares regression (PLS) method to estimate the mixing ratio and concentrations of the individual gasses. The concentration range explored in the analysis varies from a few parts per million (ppm) to thousands of ppm. Spectra obtained from HITRAN and experimental single-molecule reference spectra of each of the molecular species were acquired and used as training data sets. These spectra were used to generate simulated spectra of the gas mixtures (linear combinations of the reference spectra). Here, in this proof-of-concept experiment, we demonstrate that after an absolute calibration of the QEPAS cell, the PLS analyses could be used to determine concentrations of single molecular species with a relative accuracy within a few % for mixtures of H2O, NH3, and CH4 and with an absolute sensitivity of approximately 300 (±50) ppm/V, 50 (±5) ppm/V, and 5 (±2) ppm/V for water, ammonia, and methane, respectively. This demonstrates that QEPAS assisted by PLS is a powerful approach to estimate concentrations of individual gas components with considerable spectral overlap, which is a typical scenario for real-life adoptions and applications. Full article
(This article belongs to the Special Issue Advances in Optical Sensing, Instrumentation and Systems)
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<p>Block diagram of the main parts of the experimental setup. Actively Q-switched 1064 nm ns pump laser. QEPAS: Quartz-enhanced PAS. MIR-OPO: Mid-infrared (MIR) pulsed optical parametric oscillator. MFC: Mass-flow controller. MIR filter for removing the pump. DAQ: Signal generator for trigger signal for the 1064 nm pump laser and generating the local oscillator (both at 12,457 kHZ) for the lock-in amplifier. The downmixed signal is then acquired by an oscilloscope. The generated MIR wavelength is measured with an optical spectrometer.</p>
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<p>Training data for the PLS analysis for (<b>a</b>) water (H<math display="inline"><semantics> <msub> <mrow/> <mn>2</mn> </msub> </semantics></math>O), (<b>b</b>) ammonia (NH<math display="inline"><semantics> <msub> <mrow/> <mn>3</mn> </msub> </semantics></math>), and (<b>c</b>) methane (CH<math display="inline"><semantics> <msub> <mrow/> <mn>4</mn> </msub> </semantics></math>). The red curves show the experimental measured PAS spectra. The black curves show the spectra from the HITRAN database convolved with a Gaussian instrument profile of 5 cm<math display="inline"><semantics> <msup> <mrow/> <mrow> <mo>−</mo> <mn>1</mn> </mrow> </msup> </semantics></math>. For ammonia and methane, the R-, Q-, and P-branch are clearly observed. The y-axis is given as the measured/estimated PAS voltage and equals a concentration of 100 ppm/V for each of the three gasses. The scaling levels of the PAS signal for H<math display="inline"><semantics> <msub> <mrow/> <mn>2</mn> </msub> </semantics></math>O and NH<math display="inline"><semantics> <msub> <mrow/> <mn>3</mn> </msub> </semantics></math> are estimated using 100 ppm/V of CH<math display="inline"><semantics> <msub> <mrow/> <mn>4</mn> </msub> </semantics></math> in N<math display="inline"><semantics> <msub> <mrow/> <mn>2</mn> </msub> </semantics></math>.</p>
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<p>Test data containing a mixture of known water and methane concentrations. The red curves are the experimental PAS data, and the black curves are the HITRAN-fitted spectra with corresponding coefficients. The blue traces are the fitted PLS method with coefficients. The model was trained on combinations of 5000 experimental PAS spectra with superimposed Gaussian noise. The concentration of methane was controlled using the MFC and the water humidity was measured by the humidity sensor: (<b>a</b>) 50 ppm/V (±2.5 ppm) of methane and 5000 ppm/V (±250 ppm) of water humidity; (<b>b</b>) 25 ppm/V (±1.25 ppm) and 7500 ppm/V (±375 ppm) of absolute humidity; (<b>c</b>) 10 ppm/V (±0.5 ppm) of methane and 9000 ppm/V (±450 ppm) of absolute humidity.</p>
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<p>(<b>a</b>) Enhancement factor of the methane signal as a function of absolute humidity. Four flow settings (ratios between the methane and lab air) were used for the data: 100/0, 10/90, 25/75, and 50/50, respectively. Three different methods are used to estimate the enhancement factor, as shown with the color code. The shaded areas show the uncertainty area for the estimation of water and methane concentrations across the three different methods. The fitted blue curves are quadratic functions. (<b>b</b>) Same data as in (<b>a</b>) compensated for 2 ppm of ambient methane. Note that the uncertainty area is decreased by compensation for the ambient methane.</p>
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<p>Test data for the PLS analysis of unknown concentrations of water, ammonia, and methane. The red traces are the experimental PAS spectra, and the black are the HITRAN spectra. The HITRAN spectra are fitted with the coefficients shown in black typing. The blue traces are the fitted PLS method using the coefficients shown in blue typing. The PLS model was trained on combinations of 5000 experimental PAS spectra with a superimposed Gaussian noise (0.01).</p>
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<p>Summary of the different PLS models for estimating the unknown concentrations of (<b>a</b>) water, (<b>b</b>) ammonia, and (<b>c</b>) methane. The black columns are the fitted coefficients for the HITRAN spectra for comparison. Red columns: PLS trained on experimental PAS spectra. Blue columns: mix of HITRAN and experimental spectra. Green columns: HITRAN spectra. The error bars are given by the estimated measurement and systematic uncertainties.</p>
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13 pages, 4222 KiB  
Article
A Miniaturized 3D-Printed Quartz-Enhanced Photoacoustic Spectroscopy Sensor for Methane Detection with a High-Power Diode Laser
by Yanjun Chen, Tiantian Liang, Shunda Qiao and Yufei Ma
Sensors 2023, 23(8), 4034; https://doi.org/10.3390/s23084034 - 17 Apr 2023
Cited by 7 | Viewed by 2148
Abstract
In this invited paper, a highly sensitive methane (CH4) trace gas sensor based on quartz-enhanced photoacoustic spectroscopy (QEPAS) technique using a high-power diode laser and a miniaturized 3D-printed acoustic detection unit (ADU) is demonstrated for the first time. A high-power diode [...] Read more.
In this invited paper, a highly sensitive methane (CH4) trace gas sensor based on quartz-enhanced photoacoustic spectroscopy (QEPAS) technique using a high-power diode laser and a miniaturized 3D-printed acoustic detection unit (ADU) is demonstrated for the first time. A high-power diode laser emitting at 6057.10 cm−1 (1650.96 nm), with the optical power up to 38 mW, was selected as the excitation source to provide a strong excitation. A 3D-printed ADU, including the optical and photoacoustic detection elements, had a dimension of 42 mm, 27 mm, and 8 mm in length, width, and height, respectively. The total weight of this 3D-printed ADU, including all elements, was 6 g. A quartz tuning fork (QTF) with a resonant frequency and Q factor of 32.749 kHz and 10,598, respectively, was used as an acoustic transducer. The performance of the high-power diode laser-based CH4–QEPAS sensor, with 3D-printed ADU, was investigated in detail. The optimum laser wavelength modulation depth was found to be 0.302 cm−1. The concentration response of this CH4–QEPAS sensor was researched when the CH4 gas sample, with different concentration samples, was adopted. The obtained results showed that this CH4–QEPAS sensor had an outstanding linear concentration response. The minimum detection limit (MDL) was found to be 14.93 ppm. The normalized noise equivalent absorption (NNEA) coefficient was obtained as 2.20 × 10−7 cm−1W/Hz−1/2. A highly sensitive CH4–QEPAS sensor, with a small volume and light weight of ADU, is advantageous for the real applications. It can be portable and carried on some platforms, such as an unmanned aerial vehicle (UAV) and a balloon. Full article
(This article belongs to the Special Issue Important Achievements in Optical Measurements in China 2022–2023)
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<p>The schematic diagram of QEPAS.</p>
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<p>Absorption lines of CH<sub>4</sub>, H<sub>2</sub>O and CO<sub>2</sub> at the conditions of 1 atm pressure, 296 K temperature and 1 cm optical absorption length using the database of HITRAN 2016.</p>
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<p>The output performance of the 6057.10 cm<sup>−1</sup> CW-DFB laser. (<b>a</b>) The trend of laser output wavelength. (<b>b</b>) The laser output power. (<b>c</b>) The emission spectrum of the 6057.10 cm<sup>−1</sup> CW-DFB laser.</p>
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<p>The output performance of the 6057.10 cm<sup>−1</sup> CW-DFB laser. (<b>a</b>) The trend of laser output wavelength. (<b>b</b>) The laser output power. (<b>c</b>) The emission spectrum of the 6057.10 cm<sup>−1</sup> CW-DFB laser.</p>
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<p>Schematic diagram of 3D-printed ADU: (<b>a</b>) design pattern; (<b>b</b>) assembled ADU.</p>
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<p>Schematic diagram of CH<sub>4</sub>-QEPAS sensor with 3D-printed ADU.</p>
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<p>Frequency response of the used QTF.</p>
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<p>The 2<span class="html-italic">f</span> signal versus diode laser wavelength modulation depth for CH<sub>4</sub>-QEPAS sensor with 3D-printed ADU.</p>
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<p>2<span class="html-italic">f</span> signal for CH<sub>4</sub>-QEPAS sensor with different CH<sub>4</sub> concentrations.</p>
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<p>Concentration response of CH<sub>4</sub>-QEPAS sensor with 3D-printed ADU.</p>
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<p>Noise level of CH<sub>4</sub>-QEPAS sensor with 3D-printed ADU.</p>
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13 pages, 3645 KiB  
Article
Highly Sensitive Capacitive MEMS for Photoacoustic Gas Trace Detection
by Tarek Seoudi, Julien Charensol, Wioletta Trzpil, Fanny Pages, Diba Ayache, Roman Rousseau, Aurore Vicet and Michael Bahriz
Sensors 2023, 23(6), 3280; https://doi.org/10.3390/s23063280 - 20 Mar 2023
Cited by 2 | Viewed by 2414
Abstract
An enhanced MEMS capacitive sensor is developed for photoacoustic gas detection. This work attempts to address the lack of the literature regarding integrated and compact silicon-based photoacoustic gas sensors. The proposed mechanical resonator combines the advantages of silicon technology used in MEMS microphones [...] Read more.
An enhanced MEMS capacitive sensor is developed for photoacoustic gas detection. This work attempts to address the lack of the literature regarding integrated and compact silicon-based photoacoustic gas sensors. The proposed mechanical resonator combines the advantages of silicon technology used in MEMS microphones and the high-quality factor, characteristic of quartz tuning fork (QTF). The suggested design focuses on a functional partitioning of the structure to simultaneously enhance the collection of the photoacoustic energy, overcome viscous damping, and provide high nominal capacitance. The sensor is modeled and fabricated using silicon-on-insulator (SOI) wafers. First, an electrical characterization is performed to evaluate the resonator frequency response and nominal capacitance. Then, under photoacoustic excitation and without using an acoustic cavity, the viability and the linearity of the sensor are demonstrated by performing measurements on calibrated concentrations of methane in dry nitrogen. In the first harmonic detection, the limit of detection (LOD) is 104 ppmv (for 1 s integration time), leading to a normalized noise equivalent absorption coefficient (NNEA) of 8.6 ⋅ 10−8 Wcm−1 Hz−1/2, which is better than that of bare Quartz-Enhanced Photoacoustic Spectroscopy (QEPAS), a state-of-the-art reference to compact and selective gas sensors. Full article
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<p>Schematic illustration of H-square resonator deflection under photoacoustic excitation. The resonator is divided in two parts: the center part dedicated to the photoacoustic energy collection and the arms dedicated to the capacitive transduction. The optical axis of the laser beam is set perpendicular to the resonator and focalized on its middle. The acoustic wave is generated due to the absorption of modulated laser light.</p>
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<p>(<b>a</b>) Simulation results of first mode of vibration of H-square resonator obtained by using COMSOL Multiphysics. (<b>b</b>) Scanning electron microscopy image of the silicon-based micro-mechanical resonator (H-square resonator) with its aluminum wire bonding. The resonator dimensions are the following: length 8530 μm, width 805 μm, and thickness 75 μm.</p>
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<p>Electrical characterization circuit. <math display="inline"><semantics> <mrow> <msub> <mi>V</mi> <mrow> <mi>D</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math>, <math display="inline"><semantics> <mrow> <msub> <mi>V</mi> <mrow> <mi>A</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math>, <math display="inline"><semantics> <mrow> <msub> <mi>V</mi> <mrow> <mi>e</mi> <mi>x</mi> <mi>c</mi> </mrow> </msub> </mrow> </semantics></math><sub>,</sub> and <math display="inline"><semantics> <mrow> <msub> <mi>V</mi> <mrow> <mi>o</mi> <mi>u</mi> <mi>t</mi> </mrow> </msub> </mrow> </semantics></math> are the polarization voltage, the drive voltage, excitation voltage, and the output voltage, respectively. The output current <math display="inline"><semantics> <mrow> <msub> <mi>i</mi> <mrow> <mi>o</mi> <mi>u</mi> <mi>t</mi> </mrow> </msub> </mrow> </semantics></math> is composed of <math display="inline"><semantics> <mrow> <msub> <mi>i</mi> <mrow> <mi>r</mi> <mi>e</mi> <mi>s</mi> </mrow> </msub> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <msub> <mi>i</mi> <mrow> <mi>C</mi> <mn>0</mn> </mrow> </msub> </mrow> </semantics></math>, which are the currents passing through the <span class="html-italic">RLC</span> and <math display="inline"><semantics> <mrow> <msub> <mi>C</mi> <mn>0</mn> </msub> </mrow> </semantics></math> branch.</p>
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<p>The electrical admittance variation as function of the frequency for a 25 mV drive voltage and for different polarization voltages of 5, 10, 15, and 17.5 V. The lines represent the fitted curves while points are the experimental data.</p>
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<p>Schematic of the MEMPAS setup for methane detection [<a href="#B11-sensors-23-03280" class="html-bibr">11</a>].</p>
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<p>Absorption spectrum of methane (black curve) measured using a photodiode and the photoacoustic signal detected via the capacitive response of H-square resonator in 1f (dark-blue) and 2f (light-blue) modes at 1% of CH<sub>4</sub> at atmospheric pressure using a DFB laser emitting around 2.3 μm with an output power of 3.9 mW (at 140 mA).</p>
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<p>Displacement extracted from LDV measurement at the center and the left and right extremities of the H-square resonator at 1% of CH<sub>4</sub>. Polytec OVF-5000 LDV using VD-06 decoder, 2 mm/s/V range.</p>
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<p>(<b>a</b>) H-square signal at the first harmonic (1f) during a gas step cycle, with concentration ranging from 100 ppmv to 2000 ppmv and at 10,000 ppmv. The calibrated dilution of methane is injected for 10 min, then the cell is flushed with pure N<sub>2</sub> for 10 min. The integration time is set to 1 s. (<b>b</b>) H-resonator signals as a function of the injected methane concentration. The calibration curve is obtained by applying a linear fit.</p>
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<p>Allan–Werle deviation calculated from a 60 min acquisition for the 1f and 2f mode with 1% of CH<sub>4</sub> concentration and time constant of 100 ms.</p>
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10 pages, 1805 KiB  
Article
Commercial and Custom Quartz Tuning Forks for Quartz Enhanced Photoacoustic Spectroscopy: Stability under Humidity Variation
by Diba Ayache, Roman Rousseau, Elena Kniazeva, Julien Charensol, Tarek Seoudi, Michael Bahriz, Fares Gouzi, Vincenzo Spagnolo and Aurore Vicet
Sensors 2023, 23(6), 3135; https://doi.org/10.3390/s23063135 - 15 Mar 2023
Cited by 4 | Viewed by 1840
Abstract
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. [...] Read more.
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. Full article
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<p>The frequency response of the shift-free QEPAS signal (black) is represented. It is a Lorentzian curve centered at 32,768 Hz, having a quality factor of 8000. The QEPAS signal reaches a maximum value at <span class="html-italic">f = f</span><sub>0</sub>. The frequency response is also shown for a frequency shift of 0.28 Hz (green) and Q-factor reduction of 80 (blue). The two curves intersect (red dot) at <span class="html-italic">f = f</span><sub>0</sub>, corresponding to a 1% QEPAS signal error as calculated.</p>
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<p>From left to right a sample of each QTF is presented: AV-08, T1-08, commercial.</p>
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<p>Measured QTF parameters as a function of the excitation frequency (<b>a</b>) and the excitation amplitude (<b>b</b>). The hatched areas correspond to the target accuracy and the error bars to the standard deviation. The excitation time t<sub>exc</sub> is set to 200 ms to ensure the QTF is at steady state before the onset of the relaxation.</p>
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<p>Frequency and quality factor measurement for different humidity steps with a fixed temperature of 22 °C. Humidity and temperature data were collected from the humidity chamber software. Variation of <span class="html-italic">f</span><sub>0</sub> and Q were measured with a LabVIEW program. (<b>a</b>) commercial QTF, (<b>b</b>) AV-08 and (<b>c</b>) T1-08. The time constant of the LIA was set to 1 ms for proper BF demodulation. The study of <span class="html-italic">f</span><sub>0</sub> and Q variation for different steps of humidity was performed in two conditions described in blue and orange dashed lines (<a href="#sensors-23-03135-f004" class="html-fig">Figure 4</a>a).</p>
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21 pages, 8119 KiB  
Article
Signal-to-Noise Ratio Analysis for the Voltage-Mode Read-Out of Quartz Tuning Forks in QEPAS Applications
by Michele Di Gioia, Luigi Lombardi, Cristoforo Marzocca, Gianvito Matarrese, Giansergio Menduni, Pietro Patimisco and Vincenzo Spagnolo
Micromachines 2023, 14(3), 619; https://doi.org/10.3390/mi14030619 - 8 Mar 2023
Cited by 3 | Viewed by 1632
Abstract
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Micro/Nanophotonic Devices in Europe)
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<p>QTF read-out by means of a transimpedance preamplifier.</p>
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<p>Voltage-mode read-out of the QTF (OPAMP in non-inverting configuration).</p>
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<p>Butterworth–Van Dyke model for the QTF in the voltage-mode read-out circuit.</p>
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<p>Comparison between SPICE simulations and analytical model in Equation (2) of the frequency response of the circuit in <a href="#micromachines-14-00619-f003" class="html-fig">Figure 3</a> for R<sub>L</sub> = 100 kΩ, 0.5 MΩ and 2.5 MΩ.</p>
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<p>Peak frequency f<sub>peak</sub> of |H<sub>v</sub>|<sup>2</sup> as a function of R<sub>L</sub>.</p>
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<p>Behavior of Den1(f) and Den2(f) in Equation (3) as a function of frequency for (<b>a</b>) R<sub>L</sub> = 100 kΩ and (<b>b</b>) R<sub>L</sub> = 10 MΩ.</p>
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<p>Behavior of Den1(f) and Den2(f) in Equation (3) as a function of frequency for (<b>a</b>) R<sub>L</sub> = 100 kΩ and (<b>b</b>) R<sub>L</sub> = 10 MΩ.</p>
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<p>Peak value of |H<sub>v</sub>|<sup>2</sup> as a function of R<sub>L</sub>.</p>
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<p>Noise contributions in the circuit of <a href="#micromachines-14-00619-f003" class="html-fig">Figure 3</a>.</p>
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<p>Comparison between SPICE simulations and analytical model described in Equation (7) of the output noise spectral density contribution from the thermal noise of R<sub>L</sub>, for four different values of the resistor: 100 kΩ, 500 kΩ, 6 MΩ, and 20 MΩ.</p>
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<p>Peak of the output noise spectral density contribution due to R<sub>L</sub> as a function of R<sub>L</sub> itself.</p>
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<p>Fitting between the analytical model and SPICE simulations of the input equivalent noise current of the AD8067.</p>
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<p>Contributions to the overall output noise spectral density due to the OPAMP and resistors R<sub>p</sub> and R<sub>L</sub>, for (<b>a</b>) R<sub>L</sub> = 100 kΩ, (<b>b</b>) R<sub>L</sub> = 500 kΩ, (<b>c</b>) R<sub>L</sub> = 6 MΩ, (<b>d</b>) R<sub>L</sub> = 20 MΩ: comparison between the results obtained with the analytical model and SPICE simulations.</p>
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<p>Contributions to the overall output noise spectral density due to the OPAMP and resistors R<sub>p</sub> and R<sub>L</sub>, for (<b>a</b>) R<sub>L</sub> = 100 kΩ, (<b>b</b>) R<sub>L</sub> = 500 kΩ, (<b>c</b>) R<sub>L</sub> = 6 MΩ, (<b>d</b>) R<sub>L</sub> = 20 MΩ: comparison between the results obtained with the analytical model and SPICE simulations.</p>
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<p>Integration of the contribution S<sub>np</sub> (red line), due to R<sub>P</sub>, to the total output spectral noise density at a low-pass filter bandwidth of 0.5 Hz around the operating frequency f<sub>op</sub>, for f<sub>op</sub> = f<sub>peak</sub> and f<sub>op</sub> ≠ f<sub>peak</sub> (R<sub>L</sub> = 100 kΩ).</p>
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<p>R<sub>P</sub> noise contribution to the SNR<sub>n</sub> at the LIA output as a function of the operating frequency, for different values of R<sub>L</sub> and at a low-pass filter bandwidth of BW = 0.5 Hz.</p>
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<p>R<sub>L</sub> noise contribution to the SNR<sub>n</sub> at the LIA output as a function of the operating frequency, for different values of R<sub>L</sub> and at a low-pass filter bandwidth of BW = 0.5 Hz.</p>
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<p>Total normalized signal-to-noise ratio SNR<sub>n</sub> at the LIA output as a function of the operating frequency, for different values of R<sub>L</sub> and at a low-pass filter bandwidth of BW = 0.5 Hz. The corresponding results of SPICE simulations are also reported.</p>
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<p>R<sub>P</sub> noise contribution to the SNR<sub>n</sub> at the LIA output as a function of the operating frequency, for different values of R<sub>L</sub> and at a low-pass filter bandwidth of BW = 5 Hz.</p>
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<p>R<sub>L</sub> noise contribution to the SNR<sub>n</sub> at the LIA output as a function of the operating frequency, for different values of R<sub>L</sub> and at a low-pass filter bandwidth of BW = 5 Hz.</p>
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<p>Total normalized signal-to-noise ratio SNR<sub>n</sub> at the LIA output as a function of the operating frequency, for different values of R<sub>L</sub> and at a low-pass filter bandwidth of BW = 5 Hz. The corresponding results of SPICE simulations are also reported.</p>
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9 pages, 2664 KiB  
Communication
Simultaneous Detection of Gas Concentration and Light Intensity Based on Dual-Quartz-Enhanced Photoacoustic-Photothermal Spectroscopy
by Hao Liu, Xiang Chen, Lu Yao, Zhenyu Xu, Mai Hu and Ruifeng Kan
Photonics 2023, 10(2), 165; https://doi.org/10.3390/photonics10020165 - 4 Feb 2023
Cited by 1 | Viewed by 1518
Abstract
This research proposes a method for the simultaneous acquisition of the second harmonic (2f) signal of quartz-enhanced photoacoustic spectroscopy (QEPAS) and the first harmonic (1f) signal of quartz-enhanced photothermal spectroscopy (QEPTS) based on the dual-quartz-enhanced photoacoustic–photothermal spectroscopy. The laser [...] Read more.
This research proposes a method for the simultaneous acquisition of the second harmonic (2f) signal of quartz-enhanced photoacoustic spectroscopy (QEPAS) and the first harmonic (1f) signal of quartz-enhanced photothermal spectroscopy (QEPTS) based on the dual-quartz-enhanced photoacoustic–photothermal spectroscopy. The laser beam is first wavelength-modulated by the injection current and then intensity-modulated by an acoustic-optic modulator. The frequency of the wavelength modulation is half of the QTF1 resonant frequency, and the frequency of the intensity modulation is equal to the QTF2 resonant frequency. A modulated laser beam traveled through the two arms of the QTF1 and converged on the root of the QTF2. The 2f photoacoustic and 1f photothermal signals are concurrently obtained using the frequency division multiplexing technology and lock-in amplifiers, which allows the simultaneous detection of the gas concentration and laser light intensity. CH4 is chosen as the target gas, and the variations of the 2f photoacoustic and 1f photothermal signals are evaluated at various gas concentrations and light intensities. According to the experiments, the amplitude of the 1f photothermal signal has a good linear connection with light intensity (R2 = 0.998), which can be utilized to accurately revise the 2f photoacoustic signal while light intensity fluctuates. Over a wide range of concentrations, the normalized 2f photoacoustic signals exhibit an excellent linear response (R2 = 0.996). According to the Allan deviation analysis, the minimum detection limit for CH4 is 0.39 ppm when the integration time is 430 s. Compared with the light intensity correction using a photodetector for the QEPAS system, this approach offers a novel and effective light intensity correction method for concentration measurements employing 2f analysis. It also has the advantages of low cost and compact volume, especially for mid-infrared and terahertz systems. Full article
(This article belongs to the Special Issue Emerging Frontiers in Photoacoustic Spectroscopy Detection)
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<p>Schematic diagram of the experimental setup. AOM: acousto-optic modulator; OA: fiber optic attenuator; and FC: fiber collimator.</p>
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<p>Response frequency curve of two QTFs measured by the electrical excitation method.</p>
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<p>The amplitude of the 2<span class="html-italic">f</span> photoacoustic signal relative to the modulation depth of the laser.</p>
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<p>QEPAS system measurements at different light intensities. (<b>a</b>) The 2<span class="html-italic">f</span> photoacoustic signal at different light intensities; and (<b>b</b>) linear fitting curve of the amplitude of the 2<span class="html-italic">f</span> photoacoustic signal at different light intensities.</p>
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<p>QEPTS system measurements at different light intensities. (<b>a</b>) The 1<span class="html-italic">f</span> photothermal signal at different light intensities; and (<b>b</b>) linear fitting curve of the amplitude of the 1<span class="html-italic">f</span> photothermal signal at different light intensities.</p>
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<p>The amplitude of normalized the 2<span class="html-italic">f</span> photoacoustic signal relative to light intensities.</p>
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<p>The system measured different concentrations of target gases. (<b>a</b>) The 2<span class="html-italic">f</span> photoacoustic signal at different gas concentrations; (<b>b</b>) the 1<span class="html-italic">f</span> photothermal signal at different gas concentrations; and (<b>c</b>) the relationship between the amplitude of the normalized 2<span class="html-italic">f</span> photoacoustic signal and target gas concentrations.</p>
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<p>Allan deviation analysis of the amplitude of normalized 2<span class="html-italic">f</span> photoacoustic signal.</p>
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10 pages, 1124 KiB  
Communication
The Prevalence of Escherichia coli Derived from Bovine Clinical Mastitis and Distribution of Resistance to Antimicrobials in Part of Jiangsu Province, China
by Tianle Xu, Wendi Cao, Yicai Huang, Jingwen Zhao, Xinyue Wu and Zhangping Yang
Agriculture 2023, 13(1), 90; https://doi.org/10.3390/agriculture13010090 - 29 Dec 2022
Cited by 4 | Viewed by 2707
Abstract
Bovine mastitis is often taken as one of the most common diseases in dairy farms, which its pathophysiology leads to a reduction of milk production and its quality. The penetration of pathogenic bacteria into the mammary gland, through either a contagious or environmental [...] Read more.
Bovine mastitis is often taken as one of the most common diseases in dairy farms, which its pathophysiology leads to a reduction of milk production and its quality. The penetration of pathogenic bacteria into the mammary gland, through either a contagious or environmental approach, has been determined the way of infection. The mastitis derived bacteria have become a challenge in practice, since the increasing exposure of antimicrobial. In order to identify characteristics of the epidemiological regulation and drug resistance of the pathogenic bacteria of bovine mastitis in northern Jiangsu, 156 clinical mastitis milk samples were collected from 3 large-scale farms for the epidemiological investigation and analysis of the drug resistance of E. coli. The bacteria were positively isolated in a total of 143 milk samples. The results showed that 78 strains of E. coli were detected, with a prevalence rate of 26.99%, followed by 67 strains of K. pneumoniae, with a prevalence of 23.19%, and 38 strains of Staphylococcus, with a prevalence of spp. 13.15%. In addition, 78 strains of E. coli isolated from bovine mastitis were tested for susceptibility to 8 kinds of antibiotics. It was shown that gentamicin and tetracycline were the most effective against E. coli, with the susceptibility rate of 83.3%, followed by streptomycin and ciprofloxacin, with 73.1% and 71.8% respectively. However, β-lactams including penicillin, cefothiophene, and amoxicillin showed serious resistance to E. coli isolates. There were 12 drug resistance genes detected by PCR, including β-lactam (blaTEM, blaCTX-M, and blaSHV), aminoglycoside (armA and armB), tetracycline (tetA, tetB, and tetC), and quinolone (qnrS, qepA, oqxA, and oqxB) related genes. Notably, all E. coli isolates carried blaTEM gene (100%). The detection rate of blaCTX-M was 53.8%, followed by the detection of blaSHV (20.5%), armA (9.0%), tetA (26.9%), tetB (2.6%), tetC (20.5%), qnrS (29.5%), oqxA (37.2%) and oqxB (1.3%). The present study provides crucial information on the distribution of bovine mastitis derived bacterial pathogens in Jiangsu province, as well as highlighting the antimicrobial resistance which might help to improve the efficiency of antibiotics treatment on bovine mastitis. Full article
(This article belongs to the Special Issue Breeding, Genetics and Safety Production of Dairy Cattle)
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<p>Analysis of 289 strains of pathogenic bacteria of bovine mastitis. All isolates were obtained and identified through bacterial isolation, purification, and 16S rDNA identification.</p>
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<p>Phenotypic drug-resistance proportions of <span class="html-italic">E. coli.</span> All the 78 isolates of <span class="html-italic">E. coli</span> were analyzed with 8 antimicrobial agents. The bars in green, yellow, and red indicate the antimicrobial’s susceptibility with susceptible, intermediate, and resistant, respectively.</p>
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<p>Multidrug Resistance of 78 <span class="html-italic">E. coli</span> strains to 8 Antibiotics. All 78 <span class="html-italic">E. coli</span> isolates were collected and analyzed for multi-drug resistance with tetracycline, ciprofloxacin, streptomycin, gentamycin, lincomycin, cefothiophene, amoxicilin, and penicillin.</p>
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<p>Detection of drug-resistant genes in <span class="html-italic">E. coli</span>. PCR was performed to identify the carriage of β-lactam (blaTEM, blaCTX-M, and blaSHV), aminoglycoside (armA and armB), tetracycline (tetA, tetB, and tetC), and quinolone (qnrS, qepA, oqxA, and oqxB) related genes in 78 <span class="html-italic">E. coli</span> isolates.</p>
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12 pages, 4034 KiB  
Article
Compact GC-QEPAS for On-Site Analysis of Chemical Threats
by Nicola Liberatore, Roberto Viola, Sandro Mengali, Luca Masini, Federico Zardi, Ivan Elmi and Stefano Zampolli
Sensors 2023, 23(1), 270; https://doi.org/10.3390/s23010270 - 27 Dec 2022
Cited by 7 | Viewed by 2625
Abstract
This paper reports on a compact, portable, and selective chemical sensor for hazardous vapors at trace levels, which is under development and validation within the EU project H2020 “RISEN”. Starting from the prototype developed for a previous EU project, here, we implemented an [...] Read more.
This paper reports on a compact, portable, and selective chemical sensor for hazardous vapors at trace levels, which is under development and validation within the EU project H2020 “RISEN”. Starting from the prototype developed for a previous EU project, here, we implemented an updated two-stage purge and trap vapor pre-concentration system, a more compact MEMS- based fast gas-chromatographic separation module (Compact-GC), a new miniaturized quartz-enhanced photoacoustic spectroscopy (QEPAS) detector, and a new compact laser source. The system provides two-dimensional selectivity combining GC retention time and QEPAS spectral information and was specifically designed to be rugged, portable, suitable for on-site analysis of a crime scene, with accurate response in few minutes and in the presence of strong chemical background. The main upgrades of the sensor components and functional modules will be presented in detail, and test results with VOCs, simulants of hazardous chemical agents, and drug precursors will be reported and discussed. Full article
(This article belongs to the Collection Gas Sensors)
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<p>Sensing chain of the GC-QEPAS sensor upgraded for RISEN.</p>
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<p>GC-QEPAS sensor assembled for RISEN.</p>
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<p>Compact-GC prototype (<b>a</b>) and rendering of core components (<b>b</b>).</p>
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<p>Miniaturized QEPAS cell.</p>
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<p>Composite amplifier scheme.</p>
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<p>Total absorption chromatogram (<b>a</b>) obtained for a sampled mix of acetone and DPGME; spectra measured (blue line) and corresponding best fit from database (red line) of acetone (<b>b</b>) and DPGME (<b>d</b>) at the corresponding peaks of integral absorbance. A third intermediate peak was observed, whose corresponding measured and best-fit database spectra (<b>c</b>) correspond to acetic acid.</p>
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<p>Total absorption chromatograms obtained by desorbing in air at 280 °C (<b>a</b>) or at 180 °C (<b>b</b>) vapors of acetone by means of the first-stage pre-concentrator, showing how high temperature could promote partial conversion of acetone into acetic acid.</p>
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<p>Color map (on the left) obtained by analyzing of a mix of saturated vapors of gasoline plus ~4 ppm of DMMP. The elution time is on the horizontal axis, the wavelength of acquired photoacoustic spectra is on the vertical axis, and the color bar is related to the intensity of the measured spectra. The spectrum acquired at 120 s, allowing one to identify the DMMP by comparison with the database, is plotted on the right.</p>
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<p>Analysis of BMK. (<b>a</b>): color map obtained as described in <a href="#sensors-23-00270-f008" class="html-fig">Figure 8</a>; (<b>b</b>): the corresponding total absorption chromatogram; (<b>c</b>–<b>e</b>): spectra acquired at ca. 80 s, 115 s, and 150 s, allowing one to identify acetic acid, benzaldehyde, and BMK, respectively.</p>
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<p>Analysis of a mix of DMMP, DPGME, methyl salicylate, and safrole. (<b>a</b>): color map obtained as described in <a href="#sensors-23-00270-f008" class="html-fig">Figure 8</a>; (<b>b</b>–<b>e</b>): spectra acquired at ca. 110 s, 120 s, 160 s, and 170 s, allowing one to identify DMMP, DPGME, safrole, and methyl salicylate, respectively.</p>
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