Breath ammonia detection based on tunable fiber laser photoacoustic spectroscopy

A new detection method for ammonia in high concentration of CO₂ and H₂O is reported, which uses a wavelength modulated photoacoustic spectrometer based on a near-infrared tunable erbium-doped fiber laser in combination with an optical fiber amplifier. The multi-wavelength (1522.44 nm, 1522.94 nm and 1545.05 nm) photoacoustic signal measurement is established to detect multi-spectrum signal in samples. The problem of ammonia detection in high concentration of CO₂ and H₂O is resolved at atmospheric pressure. The minimum detection limit of 16 ppb (signal-to-noise ratio = 1) in simulated breath samples (5.3% CO₂ and 6.2% H₂O (100% relative humidity at 37°C)) is achieved.     

T-shape microresonator-based quartz-enhanced photoacoustic spectroscopy for ambient methane monitoring using 3.38-μm antimonide-distributed feedback laser diode

This paper reports on the development of a gas sensor involving a newly available 3.38-μm distributed feedback laser in combination with a novel T-shape microresonator-based quartz-enhanced photoacoustic spectroscopy (T-mR QEPAS), capable of simultaneous monitoring of multi-species (such as CH₄, H₂CO, HCl, C₂H₄) using the same QEPAS spectrophone. As a first demonstration, monitoring of ambient methane (CH₄) was achieved at atmospheric pressure with a 1σ detection limit of 400 ppbv (parts per billion by volume) in an integration time of 10 s and a water vapor concentration of 1.15 vol% (11,500 ppm) in the atmosphere, which is very suitable for field measurement of CH₄ emission.     

Modulation cancellation method in laser spectroscopy

A novel spectroscopic technique based on modulation spectroscopy with two excitation sources and quartz enhanced photoacoustic spectroscopy is described. We demonstrated two potential applications of this detection technique. First, we investigated the measurement of small temperature differences in a gas mixture. In this case, a sensitivity of 30 mK in 17 sec was achieved for a C₂H₂/N₂ gas mixture with a 0.5% C₂H₂ concentration. Second, we demonstrated the detection of broadband absorbing chemical species, for which we selected hydrazine as the target molecule and achieved a detection limit of ∼1 part per million in 1 sec. In both cases, the measurements were performed with near-IR laser diodes and overtone transitions.     

Cantilever enhanced photoacoustic spectrometry: Quantitative analysis of the trace H2S produced by SF6 decomposition

As one of the key characteristic components that result from sulfur hexafluoride (SF₆) decomposition in SF₆ gas-insulated equipment, hydrogen sulfide (H₂S) can reflect the severity of the internal insulation faults and indicate whether or not such faults involve solid insulation material effectively. The decomposition of SF₆ and its reaction with other impurities to form H₂S are simulated in this study via Materials Studio. The simulation verifies that H₂S is generated only when serious faults occur in the equipment; thus, the online monitoring of the trace H₂S is highly necessary. To achieve a high detection accuracy and avoid cross interference, the spectral line R (8) of the H₂S ν₁ + ν₂ + ν₃ co-frequency absorption band is taken as the absorption line for the gas detection by online simulation based on the HITRAN on the Web. In addition, this study develops a cantilever-enhanced photoacoustic spectrometry trace gas detection platform and conducts experimental research on the quantitative detection of trace H₂S/SF₆ and H₂S/N₂. Experimental results show that the detection sensitivity of the detection platform to trace H₂S under the background gas N₂ and SF₆ is 0.84 and 1.75 μL/L, respectively, and a strong linear relationship exists between the trace H₂S concentration and its corresponding PA signal. Moreover, based on both the theoretical simulation and experiment, the influence of temperature and pressure on the detection platform is discussed and analyzed. The results indicate that the change in the PA signal amplitude decreases with an increase in the pressure or temperature of the PA cell, and the detection platform is more sensitive to pressure.     

Comparison of infrared sources for a differential photoacoustic gas detection system

A prototype of the differential photoacoustic measurement system with an optical cantilever microphone has been developed. The system is based on gas filter correlation method. The proposed system allows real-time measurement of various IR-absorbing gases from the flowing sample or in the open air. Three setups with different kind of infrared sources were carried out to study selectivity and sensitivity of the prototype and applicability of the source types with differential method. The sources were a mechanically chopped blackbody radiator, electrically chopped blackbody radiator and mechanically chopped CO₂-laser. A detection limit for C₂H₄ was estimated with all three infrared sources. Cross sensitivity and detection limits of gases CH₄, C₂H₄ and CO₂ were measured with the mechanically chopped blackbody radiator. This crossinterference matrix was also modeled using HITRAN database and completed with CO and H₂O. The measurements indicate that at least ppb-level detection of ethylene using CO₂-laser, sub-ppm level with mechanically chopped blackbody and ppm-level with electrically modulated blackbody is possible with a proposed differential system.     

QEPAS for chemical analysis of multi-component gas mixtures

A gas sensor based on quartz-enhanced photoacoustic spectroscopy and using near-infrared, fiber-coupled diode lasers as an excitation source was developed for chemical analysis of gas mixtures containing H₂S, CO₂, and CH₄ at concentrations from 0 to 100%. Analysis of physical phenomena affecting the sensor operation is performed, the sensor performance is evaluated, and simple algorithms are developed to derive concentrations of the gases from detected electrical signals.     

Impact of water vapor on 1.51 μm ammonia absorption features used in trace gas sensing applications

Water-vapor-induced pressure broadening is reported for two NH₃ absorption features at 6612.7 and 6596.4 cm⁻¹ that are exploitable for gas sensing applications at atmospheric pressure. Absorption spectra of different NH₃–H₂O–N₂ mixtures were measured at an elevated temperature of 70°C to enable high H₂O concentrations to be reached. Line parameters were determined from a fitting procedure. The significantly greater values obtained for the H₂O-broadening coefficients of the two lines compared to N₂-broadening leads to cross-sensitivity effects in NH₃ trace gas sensors based on spectroscopic techniques that are sensitive to the width of the analyzed absorption line, as is the case in a simple implementation of wavelength modulation spectroscopy or in photoacoustic spectroscopy. In such a case, cross-sensitivity results in inaccurate gas concentration retrieval when the composition of the diluting gas changes. H₂O represents a potentially significant cross-sensitivity source as its concentration may be subject to large variations, especially in high-temperature applications where concentrations up to a couple of tens of percent may be encountered. In contrast to interference which can be minimized by an appropriate choice of the analyzed transitions, cross-sensitivity affects the entire spectrum of the analyte and is thus unavoidable in the mentioned type of gas sensors.     

Simultaneous detection of trace gases using multiplexed tunable diode lasers and a photoacoustic cell containing a cantilever microphone

We report what we believe to be a novel demonstration of simultaneous detection of multiple trace gases by near-IR tunable diode laser photoacoustic spectroscopy using a cell containing a cantilever microphone. Simultaneous detection of carbon monoxide (CO), ethyne (C₂H₂), methane (CH₄) and combined carbon monoxide/carbon dioxide (CO+CO₂) in nitrogen-based gas mixtures was achieved by modulation frequency division multiplexing the outputs of four near-IR tunable diode lasers. Normalized noise-equivalent absorption coefficients of 3.4×10^?9, 3.6×10^?9 and 1.4×10^?9 cm^?1?W?Hz^?1/2 were obtained for the simultaneous detection of CO, C₂H₂ and CH₄ at atmospheric pressure. These corresponded to noise-equivalent detection limits of 249.6 ppmv (CO), 1.5 ppmv (C₂H₂) and 293.7 ppmv (CH₄) respectively over a measurement period of 2.6 s at the relevant laser power. The performance of the system was not influenced by the number of lasers deployed, the main source of noise arising from ambient acoustic effects. The results confirm that small-volume photoacoustic cells can be used with low optical power tunable diode lasers for rapid simultaneous detection of trace gases with high sensitivity and specificity.     

Ammonia trace measurements at ppb level based on near-IR photoacoustic spectroscopy

A photoacoustic sensor using a laser diode emitting near 1532 nm in combination with an erbium-doped fibre amplifier has been developed for ammonia trace gas analysis at atmospheric pressure. NH₃ concentration measurements down to 6 ppb and a noise-equivalent detection limit below 3 ppb in dry air are demonstrated. Two wavelength-modulation schemes with 1f and 2f detection using a lock-in amplifier were investigated and compared to maximise the signal-to-noise ratio. A quantitative analysis of CO₂ and H₂O interference with NH₃ is presented. Typical concentrations present in ambient air of 400 ppm CO₂ and 1.15% H₂O (50% relative humidity at 20 °C) result in a NH₃ equivalent concentration of 36 ppb and 100 ppb, respectively. PACS 42.62.Fi; 43.35.Ud; 42.55.Px     

Photoacoustic analysis of CO2 content in annual tree rings

We have used laser photoacoustic gas analysis to study the CO₂ content sorbed by the capillary porous system of annual rings in cross-sectional disks of some conifers. The measurement results showed that in most cases, the CO₂ content in gas samples extracted by the vacuum method from annual rings in the disks is higher than the CO₂ content in atmospheric air. In the disks, we observe an annual trend in the CO₂ concentration, correlating in a number of cases with a rise in atmospheric CO₂. The annual trend in the average value of the CO₂ concentration change sign from positive to negative. We hypothesize that the observed pattern for the annual distribution of CO₂ in the disks is connected with a rise in atmospheric CO₂ and a change in the concentration gradient between stem and atmospheric CO₂. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 3, pp. 477–480, May–June, 2009.     

METHOD FOR THE STUDY OF FAST VIBRATIONAL RELAXATION OF MOLECULES USING SPECTROPHONE

A technique for measuring the vibration translational relaxation time of molecular gases using the spectrophone is described. The technique is based on the measurement of the phase of natural oscillations of the microphone membrane as a function of pressure of the gas under study. These oscillations manifest themselves in a shape of the optoacoustic (OA) signal at low gas pressure in the OA cell when the absorbing molecules are excited by short laser pulses. As an example the results on the relaxation time of the v₁+3v₃ state of H₂O molecule in H₂O-H₂O and H₂O-air collisions obtained using the OA cell of various sizes are presented.     

Adsorption and diffusion behaviors of H2, H2S,NH3, CO and H2O gases molecules on MoO3 monolayer: A DFT study

Molybdenum trioxide (MoO₃) with α-phase is a promising material for gas sensing because of its high sensitivity, fast response and thermodynamic stability. To probe the mechanism of superior gas detection ability of MoO₃ monolayer, the adsorption and diffusion of H₂, H₂S, NH₃, CO and H₂O molecules on two-dimensional (2D) MoO₃ layer are studied via density functional theory (DFT) calculations. Based on calculated adsorption energies, density of states, charge transfer, diffusion barriers and diffusion coefficient, MoO₃ shows a superior sensitive and fast response to H₂ and H₂S than CO, NH₃, H₂O, which is consistent with experimental conclusions. Moreover, the response of MoO₃ to H₂S and H₂ will be obviously enhanced at high gas concentration, and the incorporation of H₂ and H₂S results in an obvious increasing in DOS near Fermi level. Our analysis provides a conceptual foundation for future design of MoO₃-based gas sensing materials.     

Near-infrared laser based cavity ringdown spectroscopy for applications in petrochemical industry

A simple, economic diode laser based cavity ringdown system for trace-gas applications in the petrochemical industry is presented. As acetylene (C₂H₂) is sometimes present as an interfering contaminant in the gas flow of ethylene (ethene, C₂H₄) in a polyethylene production process, an on-line monitoring of such traces is essential. We investigated C₂H₂–C₂H₄ mixtures in a gas-flow configuration in real time. The experimental setup consists of a near-infrared external cavity diode laser with an output power of a few mW, standard telecommunication fibers and a home-made gas cell providing a user-friendly cavity alignment. A noise-equivalent detection sensitivity of 4.5×10^-8 cm^-1 Hz^-1/2 was achieved, corresponding to a detection limit of 20 ppbV C₂H₂ in synthetic air at 100 mbar. In an actual C₂H₂–C₂H₄ gas-flow measurement the minimum detectable concentration of C₂H₂ added to the C₂H₄ gas stream (which may already contain an unknown C₂H₂ contamination) increased to 160 ppbV. Moreover, stepwise C₂H₂ concentration increments of 500 ppbV were resolved with a 1-min time resolution and an excellent linear relationship between the absorption coefficient and the concentration was found. PACS 07.07.Df; 42.62.Fi; 82.80.Gk     

Metal-doped apatitic calcium phosphates: preparation,characterization, and reactivity in the removal of hydrogen sulfide from gas phase

With the expansion of human activities, there are more and more living areas adjacent to industrial and/or agricultural activities such as chemical processes, petroleum processes, paint finishing, food processing, livestock farming, composting plants etc. Bad odor is part of several nuisances caused by industrial and/or agricultural activities. Hydrogen sulfide (H₂S) is a typical odorous molecule which causes foul odor at very low concentration. This molecule is formed in different industrial installations, in particular in coal combustion, and petrochemical refinery. The separation and/or transformation of H₂S from gas phase to odorless products are important processes for sustainable development. In this paper, we communicate the preparation of new sorbents for the sorption of H₂S from a synthetic gas effluent. These sorbents consist in an inorganic phase (hydroxyapatite) as host particles, and well-dispersed particles of a metal oxide as guest particles which are the active phase for the removal of H₂S. At room conditions, iron, lead, and zinc doped calcium phosphates were found to be effective for the removal of H₂S. The performance of the sorbents depends on preparation method and the nature of active phases. This opens new prospects for the treatment of H₂S from gas phase.     

Mechanistic study of the gas-phase chemistry during the spray deposition of Zn(O,S) films by mass spectrometry

The mass spectrometer, is a powerful tool to identify species and investigate reactions in the gas phase. In this work, the mechanism of aerosol assisted chemical vapor deposition (AACVD) of Zn(O,S) films prepared from H₂S and zinc acetylacetonate (Zn(acac)₂) precursor solutions is elucidated by mass spectrometry. The thermochemical behavior of Zn(acac)₂ is investigated by characterizing the influence of the solvent (H₂O or ethanol), the pH value of the precursor solution and the effect of the reactant H₂S, and by tracking gaseous intermediate products using mass spectrometry. Based on these results, a proton-promoted thermolysis mechanism for the AACVD Zn(O,S) film formation is then proposed, which is initiated by the hydrolysis with H₂O as the first stage, followed either by the rearrangement with an intramolecular proton or by the reaction with an extramolecular proton to produce ZnO or Zn(O,S). A real time mass tracking of the AACVD process reveals that only an adequate amount of H₂S promotes the chemical gas-phase decomposition and sulfurization process, while an excess of H₂S depletes the gaseous Zn(acac)₂ concentration and consequently reduces the film growth rate. The knowledge of the thermal decomposition process helps to optimize synthesis conditions and to adjust film properties to meet the requirement of the application in chalcopyrite or kesterite thin film solar cells.     

Multi-hydrogenated compounds monitoring in optical fibre manufacturing process by photoacoustic spectroscopy

Sub-ppm hydrogen chloride (HCl) and water vapour (H₂O) monitoring using photoacoustic spectroscopy in optical fibre manufacturing is reported. The development and performance of a sensor based on an acoustic resonant configuration is described, and on-site measurements are presented. Two DFB lasers emitting in the 1370 nm and 1740 nm range were used for the detection of H₂O and HCl, respectively. A detection limit (defined for a SNR=3) of 60 ppb for HCl and 40 ppb for H₂O was achieved. Contamination sources of the carrier gas used for the fibre preform manufacturing are identified and discussed. PACS 42.62.Fi; 43.35.Ud     

差分吸收光谱技术在工业污染源烟气排放监测中的应用

研究了差分吸收光谱技术在工业污染源烟气排放监测中的应用及实现.借助于独立的采样和前处理系统去除烟尘和水汽对光谱拟合的影响.为避免高浓度的SO2在常温下发生光解.将经前处理后的烟气加热至150℃进行测量.采用Voigt线型对SO2,NO,NO2在185-235 nm波段的吸收截面进行了展宽,获得了高温气体的标准吸收截面,并与归一化的光谱仪仪器函数进行卷积得到了光谱拟合所需的有效吸收截面.将反演结果与非分散红外分析仪的测量结果进行了实时对比,获得了较好的一致性,验证了差分吸收光谱方法高准确度测量工业污染源烟气排放的可行性.     

Experimental equipment for studies of interaction of IR-radiation with liquid hydrides of groups IV–VI elements

The complex of special experimental apparatus for studies of interaction between IR-radiation and the thermally-stable volatile inorganic hydrides of groups IV–VI elements of the 2nd, 3rd and 4th periods in the liquid state and in the liquefied gas solutions is described. The main methods of solute concentration and integral absorption coefficients measurement are considered. The results of studies of IR-radiation absorption by volatile inorganic hydrides such as SiH₄, NH₃, PH₃, AsH₃, H₂S, and H₂Se in the liquid state and in the cryogenic solutions are presented. Using intensity, frequency and IR-absorption band contour data, the main mechanisms of intermolecular interactions in these liquids are discussed.     

Spectroscopic detection of aircraft wake gases

Using the technique of limiting information-metric scales, the potential of laser IR absorption spectroscopy for detecting small gas components of aircraft wake was quantitatively analyzed. Formulas for minimum distinguishable and minimum detectable gas concentrations were derived. Calculation was carried out for SO₂, NO, and NO₂ under typical conditions near the Boeing 707 aircraft engine nozzle at altitude H = 12.2 km. Alternative IR laser spectroscopy methods for detecting various gas components in the near wake were considered. Two possibilities to improve the concentration measurement sensitivity were analyzed: (i) a decrease in the background absorption of CO₂ and H₂O and (ii) an increase in the absorption cross section of detected gas.     

Study of the Rod-Like and spherical nano-ZnO morphology on H2S removal from natural gas

The purpose of this work is to study the adsorption of H₂S from gas streams containing He and CH₄ with an emphasis on the influence of the sorbent morphology on the process of adsorption. As an example of the approach, a unique modified nano-ZnO sample with a Rod-like morphology was fabricated and comparatively studied together with a nano-spherical ZnO sample under various conditions. The objective was accomplished applying central composite design (CCD) in order to screen the effects of significant adsorption parameters obtained by Placket-Burman design. Morphology of the sorbent, temperature, space velocity and H₂S feed concentration were initially evaluated. Placket-Burman design experiments showed a wide deviation of adsorption capacity of 0.03-0.24 g H₂S/g ZnO. Results indicated that comparing other parameters Rod like morphology comparing spherical, had significant effect on all four independent H₂S adsorption parameters. Besides that, space velocity and H₂S feed concentration were found to be effective parameters on adsorption of hydrogen sulfide in the range of 4000-8000 h⁻¹ and 0.5-1 mol% respectively. Moreover, experiments revealed a negligible effect of adsorption temperature in range of 150-250 °C. The optimized condition obtained a dynamic capacity of 0.2401 g H₂S/g ZnO at space velocity 4000 h⁻¹ and H₂S feed concentration of 1 mol%. Proceeding our study by significant parameters, analysis of variance (ANOVA) displayed a high coefficient of determination (R²) value of 0.931-0.959, indicating the satisfactory adjustment of the quadratic model.