Time resolved simultaneous detection of 14NO and 15NO via mid-infrared cavity leak-out spectroscopy

We present a ring-down absorption spectrometer based on a continuous-wave CO laser in the mid-infrared spectral region near lambda = 5 microm. Using a linear ring-down cavity (length: 0.5 m) with high reflective mirrors (R = 99.988 %), we observed a noise-equivalent absorption coefficient of 3 x 10(-10) cm(-1)Hz(-1/2). This corresponds to a noise-equivalent concentration of 800 parts per trillion (ppt) for (14)NO and 40 ppt for (15)NO in 1 s averaging time. We achieve a time resolution of 1 s which allows time resolved simultaneous detection of the two N isotopes. The delta(15)N value was obtained with a precision of +/-1.2 per thousand in a sample with a NO fraction of 11 ppm. The simultaneous detection enables the use of (15)NO as a tracer molecule for endogenous biomedical processes.     

Infrared laser-spectroscopic analysis of <Superscript>14</Superscript>NO and <Superscript>15</Superscript>NO in human breath

We report on monitoring of nitric oxide (NO) traces in human breath via infrared cavity leak-out spectroscopy. Using a CO sideband laser near 5 μm wavelength and an optical cavity with two high-reflectivity mirrors (R=99.98%), the minimum detectable absorption is 2×10⁻¹⁰ cm⁻¹ Hz^1/2. This allows for spectroscopic analysis of rare NO isotopologues with unprecedented sensitivity. Application to simultaneous online detection of ¹⁴NO and ¹⁵NO in breath samples collected in the nasal cavity is described for the first time. We achieved a noise-equivalent detection limit of 7 parts per trillion for nasal ¹⁵NO (integration time: 70 s).     

Simultaneous detection of 14NO and 15NO using Faraday modulation spectroscopy

We describe a technique of simultaneous detection of ¹⁴NO and ¹⁵NO by means of Faraday Modulation Spectroscopy (FAMOS) based on a cw distributed feedback quantum cascade laser (QCL) operating near 5.4 μm. FAMOS is a spectroscopic method for selective, sensitive, and time-resolved detection of free radical molecules such as NO, in the mid-infrared spectral region. The selected spectral lines are the Q (1.5) for ¹⁵NO located at 1842.76 cm^?1 and the P (9.5) for ¹⁴NO located at 1842.93 cm^?1. The detection limit (1σ) of 6 ppb $/\sqrt{\mathrm{Hz}}$ for ¹⁵NO and 62 ppb $/\sqrt{\mathrm{Hz}}$ for ¹⁴NO has been achieved. The simultaneous detection was performed using a fast laser frequency switching between the two isotopologues with a time resolution of 2 s. The isotope ratio (δ ¹⁵N) has been determined with a precision (1σ) of 0.52‰ at 800-s averaging time for 100 ppm NO-gas with a time resolution of 2 s. δ ¹⁵N is determined after NO release from nitrite by chemical reduction with potassium iodine.     

Frequency-agile,rapid scanning spectroscopy: absorption sensitivity of 2 × 10−12 cm−1 Hz−1/2 with a tunable diode laser

We present ultrasensitive measurements of molecular absorption using frequency-agile rapid scanning, cavity ring-down spectroscopy with an external-cavity diode laser. A microwave source that drives an electro-optic phase modulator with a bandwidth of 20 GHz generates pairs of sidebands on the probe laser. The optical cavity provides for high sensitivity and filters the carrier and all but a single, selected sideband. Absorption spectra were acquired by stepping the tunable sideband from mode-to-mode of the ring-down cavity at a rate that was limited only by the cavity decay time. This approach allows for scanning rates of 8 kHz per cavity resonance, a minimum detectable absorption coefficient of 1.7 × 10^?11 cm^?1 after only 20 ms of averaging, and a noise-equivalent absorption coefficient of 1.7 × 10^?12 cm^?1 Hz^?1/2. By comparison with cavity-enhanced laser absorption spectrometers reported in the literature, the present system is, to the best of our knowledge, among the most sensitive and has by far the highest spectrum scanning rate.     

Quantum-noise-limited cavity ring-down spectroscopy

We demonstrate a heterodyne-detected cavity ring-down spectroscopy (CRDS) method that allows for a noise-equivalent absorption coefficient of 6 × 10^?14 cm^?1 Hz^?1/2, the lowest which has been reported in a CRDS measurement. It is shown that heterodyne-detected CRDS also reaches the quantum noise limit at reasonable optical powers. In addition to offering ultra-high sensitivity, this technique provides high frequency agility over a range of 2 THz in the near-infrared, which allows entire absorption bands to be recorded in minutes. As a demonstration experiment, high resolution spectra of a near-infrared carbon dioxide band have been recorded.     

Cavity-enhanced optical feedback-assisted photo-acoustic spectroscopy with a 10.4 μm external cavity quantum cascade laser

An ultra-sensitive photo-acoustic spectrometer using a 10.4 μm broadly tunable mid-IR external cavity quantum cascade laser (EC-QCL) coupled with optical feedback to an optical power buildup cavity with high reflectivity mirrors was developed and tested. A laser optical power buildup factor of 181 was achieved, which corresponds to an intra-cavity power of 9.6 W at a wavelength of 10.4 μm. With a photo-acoustic resonance cell placed inside the cavity this resulted in the noise-equivalent absorption coefficient of 1.9 × 10^?10 cm^?1 Hz^?1/2, and a normalized noise-equivalent absorption of 1.1 × 10^?11 cm^?1 W Hz^?1/2. A novel photo-acoustic signal normalization technique makes the photo-acoustic spectrometer’s response immune to changes and drifts in the EC-QCL excitation power, EC-QCL to cavity coupling efficiency and cavity mirrors aging and contamination. An automatic lock of the EC-QCL to the cavity and optical feedback phase optimization permitted long wavelength scans within the entire EC-QCL spectral tuning range.     

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.     

A compact resonant Π-shaped photoacoustic cell with low window background for gas sensing

A resonant photoacoustic cell capable of detecting the traces of gases at an amplitude-modulation regime is represented. The cell is designed so as to minimize the window background for the cell operation at a selected acoustic resonance. A compact prototype cell (the volume of acoustic cavity of ~0.2 cm³, total cell weight of 3.5 g) adapted to the narrow diffraction-limited beam of near-infrared laser is produced and examined experimentally. The noise-associated measurement error and laser-initiated signals are studied as functions of modulation frequency. The background signal and useful response to light absorption by the gas are analyzed in measurements of absorption for ammonia traces in nitrogen flow with the help of a pigtailed DFB laser diode operated near a wavelength of 1.53 µm. The performance of absorption detection and gas-leak sensing for the prototype operated at the second longitudinal acoustic resonance (the resonance frequency of ~4.38 kHz, Q-factor of ~13.9) is estimated. The noise-equivalent absorption normalized to laser-beam power, and detection bandwidth is ~1.44 × 10^?9 cm^?1 W Hz^?1/2. The amplitude of the window-background signal is equivalent to an absorption coefficient of ~2.82 × 10^?7 cm^?1.     

QCL-based TDLAS sensor for detection of NO toward emission measurements from ovarian cancer cells

The development of a sensitive sensor for detecting nitric oxide (NO) emissions from biological samples is reported. The sensor is based on tunable diode laser absorption spectroscopy (TDLAS) using a continuous wave, thermoelectrically cooled quantum cascade laser (QCL) and a 100-m astigmatic Herriot cell. A 2f-wavelength modulation spectroscopy technique was used to obtain QCL-based TDLAS NO emission measurements with an optimum signal-to-noise ratio. An absorption line at 1,900.076 cm^?1 was targeted to measure NO with a minimum detection limit of 124 ppt. Positive control measurements with the NO donor DETA NONOate were performed to determine and optimize the sensor performance for measurements of biological samples. Our measurements with NO donor show the potential suitability of the sensor for monitoring NO emission from cancer cells for biological investigations.     

NO trace gas sensor based on quartz-enhanced photoacoustic spectroscopy and external cavity quantum cascade laser

A gas sensor based on quartz-enhanced photoacoustic detection and an external cavity quantum cascade laser was realized and characterized for trace nitric oxide monitoring using the NO R(6.5) absorption doublet at 1900.075 cm⁻¹. Signal and noise dependence on gas pressure were studied to optimize sensor performance. The NO concentration resulting in a noise-equivalent signal was found to be 15 parts per billion by volume, with 100 mW optical excitation power and a data acquisition time of 5 s.     

Spectroscopic monitoring of NO traces in plants and human breath: applications and perspectives

Optical methods based on quantum cascade lasers (QCLs) are becoming popular in many life science applications. We report on two trace gas detection schemes based on continuous wave QCLs for on-line detection of nitric oxide (NO) at the sub-part-per-billion level by volume (ppbv, 1:10^?9), using wavelength modulation spectroscopy (WMS) and Faraday rotation spectroscopy (FRS) at 1894 cm^?1 and 1875.73 cm^?1, respectively. Several technical incremental steps are discussed to further improve the sensitivity of these methods. Examples are included to demonstrate the merits of WMS-based sensor: direct monitoring of NO concentrations in exhaled breath, and from plants under pathogen attack. A simple hand-held breath sampling device that allows single breath collection at various exhalation flows (15, 50, 100 and 300 mL/s, respectively) is developed for off-line measurements and validated in combination with the WMS-based sensor. Additionally, the capability of plants to remove environmental NO is presented.     

Using a DS-DBR laser for widely tunable near-infrared cavity ring-down spectroscopy

Studies into the suitability of a novel, widely tunable telecom L-band (1,563–1,613 nm) digital supermode distributed Bragg reflector (DS-DBR) laser for cavity ring-down spectroscopy (CRDS) are presented. The spectrometer comprised of a 36.6?cm long linear cavity with ring-down times varying between 19–26 μs across the 50 nm DS-DBR wavelength range due to changes in the cavity mirror reflectivities with wavelength. The potential of such a broadband, high-resolution CRD spectrometer was illustrated by investigating several transitions of CO₂ in air, a 5 % calibrated mixture and breath samples. Allan variance measurements at a single wavelength indicated an optimal minimum detectable absorption coefficient (α _min) of 3 × 10^?10 cm^?1 over 20 s.     

Mid-infrared fiber-coupled QCL-QEPAS sensor

An innovative spectroscopic system based on an external cavity quantum cascade laser (EC-QCL) coupled with a mid-infrared (mid-IR) fiber and quartz enhanced photoacoustic spectroscopy (QEPAS) is described. SF₆ has been selected as a target gas in demonstration of the system for trace gas sensing. Single mode laser delivery through the prongs of the quartz tuning fork has been obtained employing a hollow waveguide fiber with inner silver–silver iodine (Ag–AgI) coatings and internal core diameter of 300 μm. A detailed design and realization of the QCL fiber coupling and output collimator system allowed almost practically all (99.4 %) of the laser beam to be transmitted through the spectrophone module. The achieved sensitivity of the system is 50 parts per trillion in 1 s, corresponding to a record for QEPAS normalized noise-equivalent absorption of 2.7 × 10^?10 W cm^?1 Hz^?1/2.     

Compact QEPAS sensor for trace methane and ammonia detection in impure hydrogen

A compact two-gas sensor based on quartz-enhanced photoacoustic spectroscopy (QEPAS) was developed for trace methane and ammonia quantification in impure hydrogen. The sensor is equipped with a micro-resonator to confine the sound wave and enhance QEPAS signal. The normalized noise-equivalent absorption coefficients (1σ) of 2.45×10^?8 cm^?1?W/ $\sqrt{}$ Hz and 9.1×10^?9 cm^?1?W/ $\sqrt{}$ Hz for CH₄ detection at 200 Torr and NH₃ detection at 50 Torr were demonstrated with the QEPAS sensor configuration, respectively. The influence of water vapor on the CH₄ channel was also investigated.     

Single-QCL-based absorption sensor for simultaneous trace-gas detection of CH4 and N2O

A quantum cascade laser (QCL)-based absorption sensor for the simultaneous dual-species monitoring of CH₄ and N₂O was developed using a novel compact multipass gas cell (MGC). This sensor uses a thermoelectrically cooled, continuous wave, distributed feedback QCL operating at ~7.8 µm. The QCL wavelength was scanned over two neighboring CH₄ (1275.04 cm^?1) and N₂O (1274.61 cm^?1) lines at a 1 Hz repetition rate. Wavelength modulation spectroscopy (f = 10 kHz) with second harmonic (2f) detection was performed to enhance the signal-to-noise ratio. An ultra-compact MGC (16.9 cm long and a 225 ml sampling volume) was utilized to achieve an effective optical path length of 57.6 m. With such a sensor configuration, a detection limit of 5.9 ppb for CH₄ and 2.6 ppb for N₂O was achieved, respectively, at 1-s averaging time.     

Quartz-enhanced photoacoustic spectroscopy-based sensor system for sulfur dioxide detection using a CW DFB-QCL

Sulfur dioxide (SO₂) trace gas detection based on quartz-enhanced photoacoustic spectroscopy (QEPAS) using a continuous wave, distributed feedback quantum cascade laser operating at 7.24 μm was performed. Influence of water vapor addition on monitored QEPAS SO₂ signal was also investigated. A normalized noise equivalent absorption coefficient of NNEA (1σ) = 1.21 × 10^?8 cm^?1 W Hz^?1/2 was obtained for the ν ₃ SO₂ line centered at 1,380.93 cm^?1 when the gas sample was moisturized with 2.3 % H₂O. This corresponds to a minimum detection limit (1σ) of 63 parts per billion by volume for a 1 s lock-in time constant.     

Off-axis continuous-wave cavity-enhanced absorption spectroscopy of narrow-band and broadband absorbers using red diode lasers

We present an application of continuous-wave (cw) cavity-enhanced absorption spectroscopy (CEAS) with off-axis alignment geometry of the cavity and with time integration of the cavity output intensity for detection of narrow-band and broadband absorbers using single-mode red diode lasers at λ=687.1 nm and λ=662 nm, respectively. Off-axis cw CEAS was applied to kinetic studies of the nitrate radical using a broadband absorption line at λ=662 nm. A rate constant for the reaction between the nitrate radical and E-but-2-eneof (3.78±0.17)×10^-13 cm³ molecule^-1 s^-1 was measured using a discharge-flow system. A nitrate-radical noise-equivalent (1σ≡ root-mean-square variation of the signal) detection sensitivity of 5.5×10⁹ molecule cm^-3 was achieved in a flow tube with a diameter of 4 cm and for a mirror reflectivity of ∼99.9% and a lock-in amplifier time constant of 3 s. In this case, a noise-equivalent fractional absorption per one optical pass of 1.6×10^-6 was demonstrated at a detection bandwidth of 1 Hz. A wavelength-modulation technique (modulation frequency of 10 kHz) in conjunction with off-axis cw CEAS has also been used for recording 1f- and 2f-harmonic spectra of the ^RR(15) absorption of the b¹Σ_g ⁺-X³Σ_g ^- (1,0) band of molecular oxygen at =14553.947 cm^-1. Noise-equivalent fractional absorptions per one optical pass of 1.35×10^-5, 6.9×10^-7 and 1.9×10^-6 were obtained for direct detection of the time-integrated cavity output intensity, 1f- and 2f-harmonic detection, respectively, with a mirror reflectivity of ∼99.8%, a cavity length of 0.22 m and a detection bandwidth of 1 Hz. Received: 24 June 2002 / Revised version: 12 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +44-1865/275410, E-mail: vlk@physchem.ox.ac.uk     

Pulsed cavity ring-down spectroscopy of NO and NO2 in the exhaust of a diesel engine

The application of pulsed cavity ring-down spectroscopy has been demonstrated for the in situ quantitative determination of NO and NO₂ in the exhaust of a diesel engine. NO absorption has been monitored at the transition from the Χ²Π ground state to the A²Σ⁺ state at 226 nm. For NO₂, absorption bands in the spectral region from 438 nm to 450 nm were used. At the selected engine conditions, concentrations of 212±22 ppm and 29±4 ppm have been measured for NO and NO₂, respectively, in good agreement with separate chemical exhaust gas analysis. The method is sensitive enough to meet the European Euro V standard directive on NO_x emissions. This communication discusses the relatively simple setup needed for this type of measurement, the problems encountered, as well as the prospects for single-stroke, simultaneous measurements of both NO and NO₂ at the sub-ppm level. Received: 30 November 2001 / Revised version: 18 February 2002 / Published online: 14 March 2002     

Surface and Bulk Structure Characterization of Proton (3 MeV) Irradiated Polycarbonate

Polycarbonate (Makrofol‐N) thin films were irradiated with protons (3 MeV) under vacuum at room temperature with the fluence ranging from 1×10¹⁴ to 1×10¹⁵ protons cm^?2. The change in surface morphology, optical properties, degradation of the functional groups, and crystallinity of the proton‐irradiated polymers were investigated with atomic force microscopy (AFM), UV‐VIS, and Fourier‐transform infrared (FTIR) spectroscopy, and X‐ray diffraction (XRD) techniques, respectively. AFM shows that the root mean square (RMS) roughness of the irradiated polycarbonate surface increases with the increment of ion fluence. The UV‐VIS analysis revealed that in Makrofol‐N the optical band gap decreased by 30% at highest fluence of 1×10¹⁵ protons cm^?2. The band gap can be correlated to the number of carbon atoms, M, in a cluster with a modified Robertson's equation. The cluster size in the proton‐irradiated Makrofol‐N increased from 112 to 129 atoms with the increase of fluence from 1×10¹⁴ to 1×10¹⁵ protons cm^?2. FTIR spectra of proton (3 MeV) irradiated Makrofol‐N showed a strong decrease of almost all absorption bands at about 1× 10¹⁴ protons cm^?2. However, beyond a higher critical dose an increase in intensity of almost all characteristic bands was noticed. The appearance of a new peak at 3,500 cm^?1 (‐OH groups) was observed at the higher fluences in the FTIR spectra of proton‐irradiated polycarbonate. XRD measurements showed an increase of full width at half maximum (FWHM) and the average intermolecular spacing of the main peak, which may be due to the increase of chain scission and the introduction of ‐OH groups in the proton irradiated polycarbonate.     

Optical-feedback cavity-enhanced absorption spectroscopy with a quantum-cascade laser yields the lowest formaldehyde detection limit

We report on the first application of Optical Feedback-Cavity Enhanced Absorption Spectroscopy to formaldehyde trace gas analysis at mid-infrared wavelengths. A continuous-wave room-temperature, distributed-feedback quantum cascade laser emitting around 1,769 cm^?1 has been successfully coupled to an optical cavity with finesse 10,000 in an OF-CEAS spectrometer operating on the ν₂ fundamental absorption band of formaldehyde. This compact setup (easily transportable) is able to monitor H₂CO at ambient concentrations within few seconds, presently limited by the sample exchange rate. The minimum detectable absorption is 1.6 × 10^?9 cm^?1 for a single laser scan (100 ms, 100 data points), with a detectable H₂CO mixing ratio of 60 pptv at 10 Hz. The corresponding detection limit at 1 Hz is 5 × 10^?10 cm^?1, with a normalized figure of merit of 5 × 10^?11cm $^{-1}/\sqrt{\rm Hz}$ (100 data points recorded in each spectrum taken at 10 Hz rate). A preliminary Allan variance analysis shows white noise averaging down to a minimum detection limit of 5 pptv at an optimal integration time of 10 s, which is significantly better than previous results based on multi-pass or cavity-enhanced tunable QCL absorption spectroscopy.