On-line monitoring of biogenic isoprene emissions using photoacoustic spectroscopy

Isoprene (C₅H₈) is one of the most important biogenic volatile organic compounds (VOCs) in the atmosphere. To calculate the impact of isoprene on atmospheric processes models have been developed that describe the isoprene release from plants. Measurements of this release require techniques for a fast, sensitive, on-line isoprene detection. Photoacoustic (PA) spectroscopy is applied here for the first time to monitor biogenic isoprene emissions. A CO overtone PA spectrometer is used for the detection, probing the C-H stretching vibrations in the 3 to 4 μm range. This allows us to detect isoprene down to a few ppb with a time resolution of one minute in a continuous gas flow. The number of laser lines can be adjusted to meet the requirements of the respective experiment in terms of time resolution and selectivity against other possibly interfering VOCs. This results in a highly versatile instrument for the isoprene detection in biological experiments. Furthermore, the infrared fingerprint offers the potential to detect different isoprene isotopomers simultaneously, thus allowing us to carry out on-line labelling experiments. The new apparatus was used to study the light dependence of isoprene emission from Eucalyptus globulus. The results demonstrate, that the detector system is a promising tool for the study of plant gas emissions. It allows the validation of existing emission models which are important for atmospheric processes. Received: 18 March 1999 / Revised version: 23 August 1999 / Published online: 30 November 1999     

Laser-based photoacoustic ammonia sensors for industrial applications

An industrial trace-ammonia sensor based on photoacoustic spectroscopy and CO₂ lasers has been developed for measuring ammonia with a 1σ detection limit of 220 parts-per-trillion (ppt) in an integration time of 30 s. The instrument response time for measuring ammonia was 200 s, limited by adsorption effects due to the polar nature of ammonia. The minimum detectable fractional absorbance was 2.0×10^-7, and the minimum normalized detectable absorption coefficient for this system was 2.4×10^-7 W cm^-1/z. The 9R(30) transition of the CO₂ laser at 9.22 μm with 2 W of output power was used to probe the strong sR(5,K) multiplet of ammonia at the same wavelength. This sensor was demonstrated with an optically multiplexed configuration for simultaneous measurement in four cells. Received: 3 April 2002 / Revised version: 31 May 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-310/458-0171, E-mail: webber@pranalytica.com     

Resonant photoacoustic simultaneous detection of methane and ethylene by means. of a 1.63-μm diode laser

A compact multi-component trace-gas detector based on the resonant photoacoustic technique and a NIR external cavity diode laser has been developed. It has been characterized using a mixture of ethylene and methane diluted in ambient air. A spectroscopic investigation of combination bands and overtones between 5900 and 6250 cm^-1, obtained with an IR pulsed laser photoacoustic spectrometer, allowed us to find a wavelength region where the 2ν₃ overtone of CH₄ and the ν₅+ν₉ combination band of C₂H₄ show uncongested rotational lines. Using a single-mode scan of the diode laser in this region, around 6150 cm^-1, the sensitivity for the simultaneous detection of ethylene and methane is 8 ppm/mW and 40 ppm/mW respectively. Factors affecting the sensitivity and selectivity of the detection system and possible improvements suitable to reach the sub-ppm detection limit are discussed. Received: 1 August 2001 / Revised version: 28 November 2001 / Published online: 7 February 2002 An erratum to this article is available at .     

Simultaneous online detection of isoprene and isoprene-d2 using infrared photoacoustic spectroscopy

A photoacoustic spectrometer for the simultaneous detection of isoprene and the deuterated species [4,4-²H]-2-methyl-1,3-butadiene (isoprene-d₂) is presented. Using a sealed-off ¹³CO₂ laser a single-component detection limit of 400 ppt (isoprene) and 600 ppt (isoprene-d₂) was achieved. Simultaneous monitoring of both compounds allowed the detection of labelling levels down to 6% (isoprene-d₂ in total isoprene) with a time resolution of 3 min. In emission studies with Eucalyptus globulus, the deuterated precursor [4,4-²H]-1-deoxy-D-xylulose was fed to a leaf through the transpiration stream. Emission of isoprene-d₂ started as early as 10 min after application of the precursor. Received: 3 May 2002 / Revised version: 31 May 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +49-228/733474, E-mail: frank.kuehnemann@iap.uni-bonn.de     

Intracavity photoacoustic gas detection with an external cavity diode laser

The first use of an external cavity diode-laser light source in combination with a photoacoustic detector for high-sensitivity gas detection is described. This combined system is applicable for detecting gases with absorption coefficients as low as 5 x 10^–8 cm^–1 by operating the photoacoustic cell in an intracavity mode. Measurements were made on the 1.13 m absorption lines of water vapour. For quantitative measurements, it was found to be necessary to introduce a reference cell into the system.     

Photoacoustic trace-gas detection using a cw single-frequency parametric oscillator

2 H₆) at 3.34 μm using a widely tunable cw single-frequency optical parametric oscillator. The high frequency and power stability and the continuous tunability of the parametric oscillator make it ideally suited for this application. Detection sensitivities of 0.5 ppb for ethane are obtained, which is comparable to the best results previously obtained with intracavity detection using line-tunable CO overtone lasers. The flexibility and compact size of cw single-frequency parametric oscillators can lead to portable photoacoustic trace-gas detection systems for environmental monitoring and process control. Received: 28 January 1998/Revised version: 9 April 1998     

Near shot noise detection of oxygen in the A-band with vertical-cavity surface-emitting lasers

A dual-beam laser absorption spectrometer with balanced detection for high sensitivity detection of oxygen via the A-band at 760 nm is described. The 2×2 vertical-cavity surface-emitting laser arrays used for this set-up are characterized by their wavelength tuning behavior with temperature and current, amplitude modulation, side-mode suppression ratio and polarization contrast. The spectrometer performance is determined over time periods of up to 10 h using the variation in the differential absorption between two beam paths. With the R11R11 line at STP, 670 μW laser power and 200 mm-long absorption cells, we realized an excellent linearity (R=0.9999) and over a 5-min interval a record sensitivity for VCSEL-based spectrometers of 35 ppmV, corresponding to an optical density (O.D.) of 7×10^-7. For this specific set-up, this sensitivity is only a factor of 2.7 above the shot noise limit, giving us a normalized detection limit of 7.6 ppmV·m·. Over a 10-h interval we achieved a standard deviation of 65 ppmV. Received: 26 July 2000 / Revised version: 1 November 2000 / Published online: 6 December 2000     

Detection of argon and krypton traces in noble gases by diode laser absorption spectrometry

Wavelength modulation, diode laser atomic absorption spectrometry is applied to measure traces of argon and krypton in other noble gases. Strong transitions from long-lived metastable levels highly populated in a low-pressure dc discharge are induced with a standard diode laser in the spectral range around 811 nm. The detection limits achieved are in the lower ppbv range, and the residual concentrations of Kr and Ar traces in the utilized high-purity noble gases are measured. Received: 2 October 2000 / Final version: 3 May 2001 / Published online: 7 June 2001     

High-speed vertical-cavity surface-emitting laser (VCSEL) absorption spectroscopy of ammonia (NH<Subscript>3</Subscript>) near 1.54 μm

A single-frequency VCSEL has been used for the first time for high-resolution spectroscopy near 1.5 μm. The incorporated buried-tunnel-junction technology enabled the realization of a long-wavelength InGaAlAs/InP VCSEL with low threshold current (0.925 mA), high output powers (0.576 mW) and low series resistance (60 Ω). The high-speed tuning capability of the long-wavelength VCSEL was investigated and used to conduct high-speed absorption spectroscopy. The peak tuning speed was measured to be 3.4 cm^-1/μs and a 4.5-cm^-1-wide NH₃ spectrum was recorded in 2 μs. The VCSEL was used to measure highly resolved low-pressure spectra for pressures ranging from 9.6 mbar to 1 bar. The measured Doppler-broadened linewidth of 0.02 cm^-1 agrees within 3% with the theoretical calculations. The availability and various advantages of 1.3–2-μm single-frequency VCSELs as compared to edge-emitting diode lasers, such as a large current tuning range even at very high tuning frequencies, and low production costs, should significantly expand the application fields for near-infrared laser gas sensors. Received: 17 July 2002 / Revised version: 4 December 2002 / Published online: 12 May 2003 RID="*" ID="*"Corresponding author. Fax: +43-1/58801-15999, E-mail: Gerhard@Totschnig.com     

Spectroscopic detection of biological NO with a quantum cascade laser

Two configurations of a continuous wave quantum cascade distributed feedback laser-based gas sensor for the detection of NO at a parts per billion (ppb) concentration level, typical of biomedical applications, have been investigated. The laser was operated at liquid nitrogen temperature near λ=5.2 μm. In the first configuration, a 100 m optical path length multi-pass cell was employed to enhance the NO absorption. In the second configuration, a technique based on cavity-enhanced spectroscopy (CES) was utilized, with an effective path length of 670 m. Both sensors enabled simultaneous analysis of NO and CO₂ concentrations in exhaled air. The minimum detectable NO concentration was found to be 3 ppb with a multi-pass cell and 16 ppb when using CES. The two techniques are compared, and potential future developments are discussed. Received: 1 November 2000 / Revised version: 19 January 2001 / Published online: 20 April 2001     

Sub-part-per-billion detection of nitric oxide in air using a thermoelectrically cooled mid-infrared quantum cascade laser spectrometer

Non-cryogenic, laser-absorption spectroscopy in the mid-infrared has wide applications for practical detection of trace gases in the atmosphere. We report measurements of nitric oxide in air with a detection limit less than 1 nmole/mole (<1 ppbv) using a thermoelectrically cooled quantum cascade laser operated in pulsed mode at 5.26 μm and coupled to a 210-m path length multiple-pass absorption cell at reduced pressure (50 Torr). The sensitivity of the system is enhanced by operating under pulsing conditions which reduce the laser line width to 0.010 cm^-1 (300 MHz) HWHM, and by normalizing pulse-to-pulse intensity variations with temporal gating on a single HgCdTe detector. The system is demonstrated by detecting nitric oxide in outside air and comparing results to a conventional tunable diode laser spectrometer sampling from a common inlet. A detection precision of 0.12 ppb Hz^-1/2 is achieved with a liquid-nitrogen-cooled detector. This detection precision corresponds to an absorbance precision of 1×10^-5 Hz^-1/2 or an absorbance precision per unit path length of 5×10^-10 cm^-1 Hz^-1/2. A precision of 0.3 ppb Hz^-1/2 is obtained using a thermoelectrically cooled detector, which allows continuous unattended operation over extended time periods with a totally cryogen-free instrument. Received: 1 May 2002 / Revised version: 6 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-978/663-4918, E-mail: ddn@aerodyne.com     

Portable difference-frequency laser-based cavity leak-out spectrometer for trace-gas analysis

We report a portable mid-infrared spectrometer for trace-gas analysis which is based on an all-solid-state difference-frequency-generation laser. The spectrometer provides in situ absorption path lengths of more than 3 km by means of the cavity leak-out method, a cw variant of the cavity ring-down technique. The design, performance, and application of this spectrometer are presented. The light source utilizes difference-frequency generation in a periodically poled lithium niobate (PPLN) crystal pumped by two single-frequency solid-state lasers. A maximum power of 27 μW in the wavelength region near 3.3 μm is achieved using a pump power of 20 mW at 808 nm, a signal power of 660 mW at 1064 nm, and a 50-mm-long PPLN crystal. This corresponds to a conversion efficiency of 0.42 mW/(W² cm). We demonstrate that this portable laser system is suitable as a light source in a cavity leak-out spectrometer. We achieved a minimum detectable absorption coefficient of 1×10^-8/cm (integration time: 2 s), corresponding, for example, to a detection limit of 1 part per billion ethane. This compact trace-gas analyzer with high sensitivity and specificity is promising for various environmental and medical applications. Received: 8 April 2002 / Revised version: 28 May 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +49-211/811-3121, E-mail: muertz@uni-duesseldorf.de     

Ultra-sensitive mid-infrared cavity leak-out spectroscopy using a cw optical parametric oscillator

We report a portable, all-solid-state, mid-infrared spectrometer for trace-gas analysis. The light source is a continuous-wave optical parametric oscillator based on PPLN and pumped by a Nd:YAG laser at 1064 nm. The generated single-frequency idler output covers the wavelength region between 2.35 and 3.75 μm. With its narrow line width, this light source is suitable for precise trace-gas analysis with very high sensitivity. Using cavity leak-out spectroscopy we achieved a minimum detectable absorption coefficient of 1.2×10^-9 /cm (integration time: 16 s), corresponding, for example, to a detection limit of 300 parts per trillion ethane. This sensitivity and the compact design make this trace-gas analyzer a promising tool for various in situ environmental and medical applications. Received: 19 September 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +49-228/733-474, E-mail: frank.kuehnemann@iap.uni-bonn.de     

Study of photoreaction in dichromated gelatin by laser photoacoustic technique

 An experimental method to study the photochemical reaction in solid-state dichromated gelatin during exposure is proposed, in which two laser sources with different wavelengths are used to induce photoreaction and to excite photoacoustic signal, respectively. This method is to obtain the real-time characteristics during the formation of the photoreaction product. The curve is fitted using the Rosencwaig-Gersho (R-G) theory and chemical kinetics. The reaction order and the rate of reaction may be obtained by fitting the parameters. The results show that photochemical reaction in dichromated gelatin conforms to the mechanism suggested by Watanable-Westheimer, and the photosensitivity of the samples, prepared under different conditions, is dependent on the initial concentration of photoactive ions. Received: 18 April 1995/Revised version: 3 May 1996     

Simultaneous detection of methane, oxygen and water vapour utilising near-infrared diode lasers in conjunction with difference-frequency generation

An all-diode-laser-based spectrometer is used for the simultaneous detection of methane, oxygen and water vapour. This is accomplished using a 760-nm diode laser and a 980-nm diode laser in conjunction with difference-frequency generation to 3.4 μm in a periodically poled lithium niobate crystal. Each of the output wavelengths is resonant with one of the molecular species. Simultaneous recordings over a 15-m open path of laboratory air are demonstrated. The recording scheme shows the wide applicability of a diode-laser-based difference-frequency spectrometer for the detection of molecular species in different wavelength ranges. By increasing the frequency of the 760-nm diode laser and decreasing the frequency of the 980-nm diode laser, a maximum continuous tuning range in the mid infrared of 3.6 cm^-1 is achieved. This enables the recording of several methane lines at atmospheric pressure. Pressure-dependence studies of methane lineshapes are also performed in an absorption cell. An indoor-air methane background level of 3 ppm is measured. The signal-to-noise ratio in the recorded methane spectra indicates that sub-ppm detection of methane at atmospheric pressure is feasible. Received: 6 March 2000 / Revised version: 19 June 2000 / Published online: 11 October 2000     

Detection of biogenic CO production above vascular cell cultures using a near-room- temperature QC-DFB laser

We report the first application of pulsed, near-room-temperature quantum cascade laser technology to the continuous detection of biogenic CO production rates above viable cultures of vascular smooth muscle cells. A computer-controlled sequence of measurements over a 9-h period was obtained, resulting in a minimum detectable CO production of 20 ppb in a 1-m optical path above a standard cell-culture flask. Data-processing procedures for real-time monitoring of both biogenic and ambient atmospheric CO concentrations are described. Received: 24 October 2001 / Published online: 29 November 2001     

Near-infrared trace-gas sensors based on room-temperature diode lasers

2 monitor designed for field applications using room-temperature diode lasers are presented. Near-infrared DFB lasers operating at 1.57 μm and around 2.0 μm have been used for CO₂ measurements. At ambient concentration levels a resolution of more than two orders of magnitude has been demonstrated at 1.57 μm, at 2 μm the precision is in the order of 0.1 ppm CO₂, and for trace analysis a detection limit of 10 ppb has been obtained. The measurements demonstrate the capability of near-infrared DFB diode lasers for the precise determination of CO₂ concentrations as required for climatological, medical, or industrial applications. Received: 24 February 1998/Revised version: 27 April 1998     

Chemical sensing with pulsed QC-DFB lasers operating at 15.6 micrometers

Pulsed thermoelectrically cooled QC-DFB lasers operating at 15.6 μm were characterized for spectroscopic gas sensing applications. A new method for wavelength scanning based on repetition rate modulation was developed. A non-wavelength-selective pyroelectric detector was incorporated in the sensor configuration giving the advantage of room-temperature operation and low cost. Absorption lines of CO₂ and H₂O were observed in ambient air, providing information about the concentration of these species. Received: 29 April 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-713/348-5686, E-mail: akoster@rice.edu     

Far-infrared laser emission from deuterated ammonia

By optically pumping the deuterated isotopomers of ¹⁴NH₃ and ¹⁵NH₃ using ¹²C¹⁶O₂, ¹³C¹⁶O₂, ¹²C¹⁸O₂, and ¹³C¹⁸O₂ lasers, several new far-infrared (FIR) emission lines between 65 μm and 125 μm have been detected. The existing spectroscopy of ¹⁴N-ammonia isotopomers has been used to identify many of these lines, as well as some previously observed but unidentified. The spectroscopic data have been analyzed to predict over 20 additional FIR laser lines that could be pumped by a more capable CO₂ laser. This effort was motivated by a need for strong laser lines in frequency coincidence with molecular transitions of astrophysical interest. Of particularnote is the measurement of the 2680-GHz line of ¹⁴NHD₂, whose frequency is 4.9 GHz higher than that of the important J=1-0 line of interstellar HD. Received: 25 July 2002 / Published online: 20 December 2002 RID="*" ID="*"Corresponding author. Fax: +1-303/492-5941, E-mail: boreiko@spot.colorado.edu     

Fundamental noise sources in a high-sensitivity two-tone frequency modulation spectrometer and detection of CO2 at 1.6 μm and 2 μm

2 , and its sensitivity is 7(2)×10^-8 in a 1-Hz bandwidth. The corresponding minimum detectable concentration of CO₂ in air has been estimated to be 1 ppm · m. This opens the possibility of a detection at ppb levels at 2 μm, where a two orders of magnitude increase in the CO₂ absorption signal is demonstrated. Received: 06 April 1998/Revised version: 02 July 1998