Continuous wave,distributed feedback diode laser based sensor for trace-gas detection of ethane

The development of a continuous wave (CW), thermoelectrically cooled (TEC), distributed feedback (DFB) laser diode based spectroscopic trace-gas sensor for ultra-sensitive and selective ethane (C₂H₆) concentration measurements is reported. The sensor platform used tunable diode laser absorption spectroscopy (TDLAS) based on a 2f wavelength modulation (WM) detection technique. TDLAS was performed with a 100 m optical path length astigmatic Herriott cell. For an interference free C₂H₆ absorption line located at 2976.8 cm⁻¹ a 1σ minimum detection limit of 240 pptv (part per trillion by volume) with a 1 second lock-in amplifier time constant was achieved. In addition, reliable and long-term sensor performance was obtained when operating the sensor in an absorption line locked mode.     

A novel multiple species ringdown spectrometer for in situ measurements of methane,carbon dioxide,and carbon isotope

We have developed a standalone, user-friendly, multi-species ringdown spectrometer for in situ measurements of methane (CH₄), carbon dioxide (CO₂), and a carbon dioxide isotope (¹³CO₂). The instrument is based on near-infrared continuous-wave cavity ringdown spectroscopy (NIR cw-CRDS) and engineered to be of approximately 16 kg with dimensions of 50 cm × 40 cm × 15 cm. The instrument design, optical configuration, electronic control, and performance are described. CH₄, CO₂, and ¹³CO₂ are measured at different wavelengths that are obtained through multiplexing two distributed feedback laser diodes with central wavelengths at 1597 and 1650 nm. The spectrometer has low power consumption and runs for 4–6 h when powered by a standard car battery. The instrument is operated either locally by interacting with a 7-inch touch screen or remotely via an Internet connection. The 1-σ detection limits for CH₄ and CO₂ are 0.2 and 120 ppmv, respectively. The measurement uncertainty is better than ±4% of full-scale reading for CH₄ and CO₂ and ±1.5‰ for δ¹³C (part per thousand relative to the Pee Dee Belemnite scale). Measurement of each species is near real-time; switching from measuring one species to another takes less than one minute. This work demonstrates a novel multiple-species CRDS-instrumentation platform, which can be adopted for development of an array of ringdown spectrometers for portable, user-friendly, field analysis of a variety of gases in environmental and industrial applications. Discussion of a future version of the spectrometer with better detection sensitivity, higher accuracy, and a smaller geometry is also presented. PACS  42.62.Fi; 42.55.Px; 33.20.Ea; 07.88.+y; 07.57.Ty     

Space-borne remote sensing of CO2, CH4, and N2O by integrated path differential absorption lidar: a sensitivity analysis

CO₂, CH₄, and N₂O are recognised as the most important greenhouse gases, the concentrations of which increase rapidly through human activities. Space-borne integrated path differential absorption lidar allows global observations at day and night over land and water surfaces in all climates. In this study we investigate potential sources of measurement errors and compare them with the scientific requirements. Our simulations reveal that moderate-size instruments in terms of telescope aperture (0.5–1.5 m) and laser average power (0.4–4 W) potentially have a low random error of the greenhouse gas column which is 0.2% for CO₂ and 0.4% for CH₄ for soundings at 1.6 μm, 0.4% for CO₂ at 2.1 μm, 0.6% for CH₄ at 2.3 μm, and 0.3% for N₂O at 3.9 μm. Coherent detection instruments are generally limited by speckle noise, while direct detection instruments suffer from high detector noise using current technology. The wavelength selection in the vicinity of the absorption line is critical as it controls the height region of highest sensitivity, the temperature cross-sensitivity, and the demands on frequency stability. For CO₂, an error budget of 0.08% is derived from our analysis of the sources of systematic errors. Among them, the frequency stability of ± 0.3 MHz for the laser transmitter and spectral purity of 99.9% in conjunction with a narrow-band spectral filter of 1 GHz (FWHM) are identified to be challenging instrument requirements for a direct detection CO₂ system operating at 1.6 μm. PACS 42.68.Wt; 95.75.Qr     

TRISTAR – a tracer in situ TDLAS for atmospheric research

2 O during two airborne polar stratospheric campaigns in January and March 1997. These species were detected using integration periods of 1 s with a precision of ±2%(3σ) and a calibration accuracy of ±2.8% during a total of 11 measurement flights up to a maximum altitude of 12.5 km. More recently all three channels have been operated simultaneously for CO, CH₄, and N₂O with comparable results. Received: 5 March 1998     

Mid-infrared laser absorption spectrometers based upon all-diode laser difference frequency generation and a room temperature quantum cascade laser for the detection of CO, N2O and NO

We describe the performance of two mid-infrared laser spectrometers for carbon monoxide, nitrous oxide and nitric oxide detection. The first spectrometer for CO and N₂O detection around 2203 cm^-1 is based upon all-diode laser difference frequency generation (DFG) in a quasi-phase matched periodically-poled lithium niobate (PPLN) crystal using two continuous-wave room-temperature distributed feedback diode lasers at 859 and 1059 nm. We also report on the performance of a mid-infrared spectrometer for NO detection at ∼ 1900 cm^-1 based upon a thermoelectrically-cooled continuous-wave distributed feedback quantum cascade laser (QCL). Both spectrometers had a single-pass optical cell and a thermoelectrically cooled HgCdZnTe photovoltaic detector. Typical minimum detection limits of 2.8 ppmv for CO, 0.6 ppmv for N₂O and 2.7 ppmv for NO have been demonstrated for a 100 averaged spectra acquired within 1.25 s and a cell base length of 21 cm at ∼ 100 Torr. Noise-equivalent absorptions of 10^-5 and 10^-4 Hz^-1/2 are typically demonstrated for the QCL and the DFG based spectrometers, respectively. PACS  42.55.Px; 42.62.Fi; 42.65.-k; 42.72.Ai; 42.68.Ca     

Incoherent broad-band cavity-enhanced absorption spectroscopy for simultaneous trace measurements of NO2 and NO3 with a LED source

In the past decade, due to a growing awareness of the importance of air quality and air pollution control, many diagnostic tools and techniques have been developed to detect and quantify the concentration of pollutants such as NO _x , SO _x , CO, and CO₂. We present here an Incoherent Broad-Band Cavity-Enhanced Spectroscopy (IBB-CEAS) set-up which uses a LED emitting around 625 nm for the simultaneous detection of NO₂ and NO₃. The LED light transmitted through a high-finesse optical cavity filled with a gas sample is detected by a low resolution spectrometer. After calibration of the spectrometer with a NO₂ reference sample, a linear multicomponent fit analysis of the absorption spectra allows for simultaneous measurements of NO₂ and NO₃ concentrations in a flow of ambient air. The optimal averaging time is found to be on the order of 400 s and appears to be limited by the drift of the spectrometer. At this averaging time the smallest detectable absorption is 2×10⁻¹⁰ cm⁻¹, which corresponds to detection limits of 600 pptv for NO₂ and 2 pptv for NO₃. This compact and low cost instrument is a promising diagnostic tool for air quality control in urban environments.     

Chirped quantum cascade laser induced rapid passage signatures in an optically thick gas

We report observations of rapid passage signals induced in samples of N₂O and CH₄ present in a multipass cell with an optical path length of 5 m. The effect of laser power and chirp rate upon the signals has been studied by utilising two different chirped quantum cascade lasers operating around 8 μm. The rapid passage signals exhibit an increasing delay in the switch from absorption to emission as a function of increased gas pressure (up to 8 Torr of gas). By comparing a selection of transitions in N₂O and CH₄, we show that, unlike ammonia, this ‘pressure shift’ is independent of the transition dipole moment, spectroscopic branch probed and laser chirp rate. As the transition dipole moment is much larger in nitrous oxide than methane, we believe that this indicates that N₂O–N₂O collisions are more efficient at removing coherence from the polarised sample than CH₄–CH₄ collisions. We have also observed this pressure shift in a short path length of 40 cm, although with a much reduced value, indicating that propagation effects are important in this optically thick minimally damped system.     

Absolute cross sections of electron attachment to molecular clusters. Part II: Formation of (H2O) N? , (N2O) N? , and (N2) N?

Absolute cross sections σ⁻(E, N) of electron attachment to clusters (H₂O) _N , (N₂O) _N , and (N₂) _N for varying electron energy E and cluster size N are measured by using crossed electron and cluster beams in a vacuum. Continua of σ⁻(E) are found that correlate well with the functions of electron impact excitation of molecules’ internal degrees of freedom. The electron is attached through its solvation in a cluster. In the formation of (H₂O) _N ⁻ , (N₂O) _N ⁻ , and (N₂) _N ⁻ , the curves σ⁻(N) have a well-defined threshold because of a rise in the electron thermalization and solvation probability with N. For (H₂O)₉₀₀, (N₂O)₃₅₀, and (N₂)₂₆₀ clusters at E = 0.2 eV, the energy losses by the slow electron in the cluster are estimated as 3.0 × 10⁷, 2.7 × 10⁷, and 6.0 × 10⁵ eV/m, respectively. It is found that the growth of σ⁻ with N is the fastest for (H₂O) _N and (N₂) _N clusters at E → 0 as a result of polarization capture of the s-electron. Specifically, at E = 0.1 eV and N = 260, σ⁻ = 3.0 × 10⁻¹³ cm² for H₂O clusters, 8.0 × 10⁻¹⁴ cm² for N₂O clusters, and 1.4 × 10⁻¹⁵ cm² for N₂ clusters; at E = 11 eV, σ⁻ = 9.0 × 10⁻¹⁶ cm² for (H₂O)₂₀₀ clusters, 2.4 × 10⁻¹⁴ cm² for (N₂O)₃₅₀ clusters, and 5.0 × 10⁻¹⁷ cm² for (N₂)₂₆₀ clusters; finally, at E = 30 eV, σ⁻ = 3.6 × 10⁻¹⁷ cm² for (N₂O)₁₀ clusters and 3.0 × 10⁻¹⁷ cm² for (N₂)₁₂₅ clusters. Original Russian Text ? A.A. Vostrikov, D.Yu. Dubov, 2006, published in Zhurnal Tekhnicheskoĭ Fiziki, 2006, Vol. 76, No. 12, pp. 1–15.     

Pulsed quantum cascade laser instrument with compact design for rapid, high sensitivity measurements of trace gases in air

We have developed a compact instrument for sensitive, rapid and continuous measurement of trace gases in air, with results presented here for methane (CH₄), nitric oxide (NO), nitrous oxide (N₂O) and ammonia (NH₃). This instrument takes advantage of recent technology in quantum cascade (QC) lasers and infrared detectors, which allows high sensitivity without cryogenic liquids, e.g., 0.2 ppb (0.2×10^-9) of NH₃ in air in 1 s. One may substitute a QC laser operating at a different wavelength to measure other gases. The instrument operates continuously, requiring little operator attention, and web-based remote access is provided for instrument control, calibration and data retrieval. The instrument design includes a thermoelectrically (TE) cooled pulsed distributed feedback (DFB) QC laser, a low volume (0.5 l) multipass cell offering 76 m absorption path length and a TE cooled detector. Integrated software for laser control and data analysis using direct absorption provides quantitative trace gas measurements without calibration gases. The instrument may be applied to field measurements of gases of environmental concern. PACS  07.57.Ty; 42.62.Fi; 92.70.Cp     

Optimization of a compact photoacoustic quantum cascade laser spectrometer for atmospheric flux measurements: application to the detection of methane and nitrous oxide

Room temperature (RT) quantum cascade lasers (QCL) are now available even in continuous wave (cw) mode, which is very promising for in situ gas detectors. Ambient air monitoring requires high sensitivity with robust and simple apparatus. For that purpose, a compact photoacoustic setup was combined with two cw QCLs to measure ambient methane and nitrous oxide in the 8 μm range. The first laser had already been used to calibrate the sensitivity of the photoacoustic cell and a detection limit of 3 ppb of CH₄ with a 1s integration time per point was demonstrated. In situ monitoring with this laser was difficult because of liquid nitrogen cooling. The second laser is a new RT cw QCL with lower power, which enabled one to reach a detection limit of 34 ppb of methane in flow. The loss in sensitivity is mainly due to the weaker power as photoacoustic signal is proportional to light power. The calibration for methane detection leads to an estimated detection limit of 14 ppb for N₂O flux measurements. Various ways of modulation have been tested. The possibility to monitor ambient air CH₄ and N₂O at ground level with this PA spectrometer was demonstrated in flux with these QCLs. PACS 07.88; 92.60.Sz     

Flame structure of composite pseudo-propellants based on nitramines and azide polymers at high pressure

The chemical and thermal structures of flame of composite pseudo-propellants based on cyclic nitramines (HMX, RDX) and azide polymers (GAP and BAMO–AMMO copolymer) were investigated at a pressure of 1.0 MPa by molecular beam mass spectrometry and a microthermocouple technique. Eleven species H₂, H₂O, HCN, CO, CO₂, N₂, N₂O, CH₂O, NO, NO₂, and nitramine vapor (RDX_v or HMX_v), were identified, and their concentration profiles were measured in HMX/GAP and RDX/GAP pseudo-propellant flames at a pressure of 1 MPa. Two main zones of chemical reactions in the flame of nitramine/GAP pseudo-propellants were found. In the first, narrow, zone 0.1 mm wide (adjacent to the burning surface), complete consumption of nitramine vapor and NO₂ with the formation of NO, HCN, CO, H₂, and N₂ occurs. In the second, wider high-temperature zone, oxidation of HCN and CH₂O by NO and N₂O with the subsequent formation of CO, H₂, and N₂ takes place. The leading reactions in the high-temperature zone of flame of nitramine/GAP pseudo-propellants are the same as in the case of pure nitramines. In the case of nitramine/BAMO–AMMO pseudo-propellants a presence of carbonaceous particles on the burning surface did not allow us to analyze the zone adjacent to the burning surface, therefore only one flame zone was found. Temperature profiles in the combustion wave of nitramine/azide polymer pseudo-propellants were measured at 1 MPa. The data obtained can be used to develop and validate a self-sustain combustion model for pseudo-propellants based on nitramines and azide polymers.     

Relaxation effects and high sensitivity photoacoustic detection of NO<Subscript>2</Subscript> with a blue laser diode

A detection limit of 200 ppt of NO₂ in N₂ at atmospheric pressure was obtained with a photoacoustic detector and a high power blue laser diode. This corresponds to a normalized noise (1σ) equivalent absorption coefficient of 2×10^-9 cm^-1W/Hz^0.5. Measurements at different laser modulation frequencies showed no frequency dependence of the photoacoustic signal, indicating a relaxation time τ < 4 μs. Mixing O₂ into the NO₂ containing gas results in a decrease of the photoacoustic signal. A simple model shows that this effect can be attributed to an increased vibrational-vibrational relaxation of NO₂ to O₂. PACS 31.70.Hq; 34.50.Ez; 42.55.Px     

Design considerations in high-sensitivity off-axis integrated cavity output spectroscopy

Off-axis integrated cavity output spectroscopy (OA-ICOS) has generated much interest because it potentially allows highly sensitive field measurements with robust optical alignment. We discuss here design choices involved in design of an OA-ICOS instrument and how these choices impact instrument sensitivity, using as our example the design of the Harvard ICOS isotope instrument, which demonstrates the highest reported sensitivity for mid-IR OA-ICOS (2.4×10^-11 cm^-1Hz^-1/2 at 6.7 μm, obtained during measurements of water vapor isotopologues H₂O, HDO, and H₂  ¹⁸O in the laboratory and onboard NASA’s WB-57 high-altitude research aircraft). We compare the sensitivity of several OA-ICOS instruments with differing design parameters, show how comparisons are hindered by differing definitions of instrument performance metrics, and suggest a common metric of MDA_meas, the fractional absorption equivalent to 1σ uncertainty in an actual measurement, normalized to 1 s integration. We also note that despite an emphasis on sensitivity in the literature, in the Harvard ICOS isotope instrument and likely also similar instruments, systematic errors associated with fitting of the baseline laser power are of equal importance to total measurement uncertainty.     

A systematic study of J/ψ suppression in cold nuclear matter

Understanding the effects of cold nuclear matter on J/ψ production is a key requirement for interpreting the J/ψ suppression reported in heavy-ion collisions. Based on a Glauber model, the J/ψ–nucleon inelastic cross section is determined from a statistical analysis of the J/ψ world data on nuclear targets. The global fit of all data gives σ_J/ψN = 3.4 ± 0.2 mb, significantly smaller than previous estimates, yet the χ² of the fit is pretty large, χ²/ndf=1.5. A similar value, σ_J/ψN = 3.5 ± 0.2 ± 1.7 mb, is obtained when the De Florian–Sassot modifications of the nuclear parton densities are included in the analysis, although we emphasise that the present uncertainties on gluon (anti-) shadowing do not allow for a precise determination of σ_J/ψN. Finally, the possible energy dependence of the J/ψ–nucleon inelastic cross section is investigated within this framework. No significant energy dependence of the J/ψ–N interaction is observed. PACS  25.75.-q; 14.40.Gx; 24.85.+p     

Cavity ring-down spectroscopy for atmospheric trace gas detection: application to the nitrate radical (NO3)

Cavity ring-down spectroscopy is a relatively new and quite sensitive technique for the measurement of gas-phase optical extinction. It holds the potential for simple, direct and sensitive measurement of the concentrations of a variety of trace gases in the atmosphere. For example, detection of the nitrate radical, NO₃, and its companion, dinitrogen pentoxide, N₂O₅, has been demonstrated with a sensitivity of 0.25 pptv (1σ). This paper considers several of the requirements for the application of cavity ring-down spectroscopy to concentration measurements of trace gases in ambient air. These include detection sensitivity, measurement of an accurate zero in the presence of competing absorbers, cavity stability and mirror cleanliness, laser line-width effects, saturation effects, Rayleigh scattering, the influence of atmospheric aerosols and sampling issues for reactive species. Examples drawn from our work on NO₃ and N₂O₅ detection in the field illustrate these considerations. Received: 1 April 2002 / Revised version: 5 June 2002 / Published online: 12 September 2002 RID="*" ID="*"Corresponding author. Fax: +1-303/497-5822, E-mail: sbrown@al.noaa.gov     

Reactivity of surface OH in CH4 reforming reactions on Ni(1 1 1): A density functional theory calculation

The reactivity of surface OH in CH₄ reforming reactions was investigated by using density functional theory calculation. The key reaction pathway from CH₄ into syngas by surface OH follows CH₄ → CH → CHOH → CHO → CO, which is similar with the pathway induced by surface O in CO₂ reforming of CH₄ (CH₄ → CH → CHO → CO). Surface OH decreases the possibility of CH dehydrogenation into surface carbon. Compared to surface O and OH, surface H can eliminate surface carbon deposition more efficiently.     

Atomic and molecular fluorescence as a stratospheric species monitor

The results of an extensive evaluation are presented assessing the potential of atomic and molecular fluorescence as a stratospheric monitor of the concentrations of any one of eighteen minor species. These include Cl, Cl₂, ClO, ClO₂, CO, H₂, HCHO, HCl, HNO₂, HNO₃, H₂S, NH₃, NO, NO₂, N₂O, O, OH and SO₂. All spectral regions from the vacuum u.v. through to the i.r. have been included. Where appropriate, detection limits (signal/noise ratio of unity) are presented for each species under various sample pressure conditions and are based on practical systems that could be constructed using current technology.The most promising systems, with typical detection limits indicated either as parts per million, billion or trillion by volume, are for CO(5ppb), NO₂(<1ppb), OH(0.2ppt) and O(50–200ppt). The fluorescence sensitivities for Cl(0.5–1 ppt), H₂(0.2 ppm at 10 torr sample pressure) and SO₂(1–10 ppb) are marginally insufficient at present for such a stratospheric application. Likewise HCHO(10 ppb) and NO(100 ppb) fluorescence detection may be of interest in other applications where sensitivity demands are not as severe. There are no promising analytical possibilities using direct fluorescence techniques for Cl₂, ClO₂, HCl, HNO₂, HNO₃, H₂S, NH₃ or N₂O. ClO fluorescence has not yet been characterized.It has been noted, for various reasons, that i.r. fluorescence techniques in general cannot be exploited in the development of sensitive analyzers. However, by far the most surprising outcome of this study has been the recognition of the analytical potential of vacuum u.v. fluorescence. For some species, under certain conditions, extremely high sensitivities are possible even with samples in air at atmospheric pressure.     

Microwave-assisted rapid synthesis of Ag nanoparticles/graphene nanosheet composites and their application for hydrogen peroxide detection

Abstract  

Ag nanoparticles/graphene nanosheet (AgNPs/GN) composites have been rapidly prepared by a one-pot microwave-assisted reduction method, carried out by microwave irradiation of a N,N-dimethylformamide (DMF) solution of graphene oxide (GO) and AgNO₃. Several analytical techniques including UV–vis spectroscopy, FT-IR spectroscopy, Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) have been used to characterize the resulting AgNPs/GN composites. It suggests that such composites exhibit good catalytic activity toward reduction of hydrogen peroxide (H₂O₂), leading to a H₂O₂ sensor with a fast amperometric response time of less than 2 s. The linear detection range is estimated to be from 0.1 to 100 mM (r = 0.999), and the detection limit is estimated to be 0.5 μM at a signal-to-noise ratio of 3.     

Portable fiber-coupled diode-laser-based sensor for multiple trace gas detection

Tunable narrowband mid-infrared radiation from 3.25 to 4.4 μm is generated by a compact fiber-coupled, difference-frequency-based spectrosopic source. A 20-mW external cavity diode laser (with a tuning range from 814 to 870 nm) and a 50-mW distributed-Bragg-reflector diode-laser-seeded ytterbium-doped fiber amplifier operating at 1083 nm are difference-frequency mixed in a multi-grating, temperature-controlled periodically poled LiNbO₃ crystal. A conversion efficiency of 0.44 mW/(W² cm) (corresponding to a power of ≈3 μW at 3.3 μm) represents the highest conversion efficiency reported for a portable device. Performance characteristics of such a sensor and its application to spectroscopic detection of CO₂, N₂O, H₂CO, HCl, NO₂, and CH₄ will be reported in this work. Received: 14 May / Revised version: 24 June 1999 / Published online: 30 September 1999     

Sigma Terms of Light-Quark Hadrons

A calculation of the current-quark mass dependence of hadron masses can help in using observational data to place constraints on the variation of nature’s fundamental parameters. A hadron’s σ-term is a measure of this dependence. The connection between a hadron’s σ-term and the Feynman-Hellmann theorem is illustrated with an explicit calculation for the pion using a rainbow-ladder truncation of the Dyson-Schwinger equations: in the vicinity of the chiral limit σ_π = m_π/2. This truncation also provides a decent estimate of σ_ρ because the two dominant self-energy corrections to the ρ-meson’s mass largely cancel in their contribution to σ_ρ. The truncation is less accurate for the ω, however, because there is little to compete with an ω → ρπ self-energy contribution that magnifies the value of σ_ω by ≲25%. A Poincaré-covariant Faddeev equation, which describes baryons as composites of confined-quarks and -nonpointlike-diquarks, is solved to obtain the current-quark mass dependence of the masses of the nucleon and Δ, and thereby σ_N and σ_Δ. This “quark-core” piece is augmented by the “pion cloud” contribution, which is positive. The analysis yields σ_N ≃ 60 MeV and σ_Δ ≃ 50 MeV.