Albert Manninen

Novel laser spectroscopic technique for continuous analysis of N2O isotopomers--application and intercomparison with isotope ratio mass spectrometry.

RATIONALE Nitrous oxide (N(2)O), a highly climate-relevant trace gas, is mainly derived from microbial denitrification and nitrification processes in soils. Apportioning N(2)O to these source processes is a challenging task, but better understanding of the processes is required to improve mitigation strategies. The N(2)O site-specific (15)N signatures from denitrification and nitrification have been shown to be clearly different, making this signature a potential tool for N(2)O source identification. We have applied for the first time quantum cascade laser absorption spectroscopy (QCLAS) for the continuous analysis of the intramolecular (15)N distribution of soil-derived N(2)O and compared this with state-of-the-art isotope ratio mass spectrometry (IRMS). METHODS Soil was amended with nitrate and sucrose and incubated in a laboratory setup. The N(2)O release was quantified by FTIR spectroscopy, while the N(2)O intramolecular (15)N distribution was continuously analyzed by online QCLAS at 1 Hz resolution. The QCLAS results on time-integrating flask samples were compared with those from the IRMS analysis. RESULTS The analytical precision (2σ) of QCLAS was around 0.3‰ for the δ(15)N(bulk) and the (15)N site preference (SP) for 1-min average values. Comparing the two techniques on flask samples, excellent agreement (R(2)= 0.99; offset of 1.2‰) was observed for the δ(15)N(bulk) values while for the SP values the correlation was less good (R(2 )= 0.76; offset of 0.9‰), presumably due to the lower precision of the IRMS SP measurements. CONCLUSIONS These findings validate QCLAS as a viable alternative technique with even higher precision than state-of-the-art IRMS. Thus, laser spectroscopy has the potential to contribute significantly to a better understanding of N turnover in soils, which is crucial for advancing strategies to mitigate emissions of this efficient greenhouse gas.

Compact multipass optical cell for laser spectroscopy

A multipass cell (MPC) design for laser absorption spectroscopy is presented. The development of this new type of optical cell was driven by stringent criteria for compactness, robustness, low volume, and ease of use in optical systems. A single piece of reflective toroidal surface forms a near-concentric cavity with a volume of merely 40 cm(3). Contrary to traditional MPCs, this design allows for flexible path-length adjustments by simply changing the aiming angle of the laser beam at the entrance window. Two effective optical path lengths of 2.2 and 4.1 m were chosen to demonstrate the cells suitability for high-precision isotope ratio measurements of CO(2) at 1% and ambient mixing ratio levels.

Instrumentation for measuring fluorescence cross sections from airborne microsized particles

An experimental instrument for measuring a laser-induced fluorescence spectrum from a single aerosol particle is described. As a demonstration of instrument capabilities, the results of monodisperse 4.7 microm sodium chloride particles doped with fluorescent riboflavin, produced with an inkjet aerosol generator, are presented. The fluorescence of the aerosol particles is excited in the wide range from 210 to 419 nm using a pulsed, tunable optical parametric oscillator laser. The maximum of the fluorescence emission of separately measured particles is detected at 560 nm. The dependence of the fluorescence on the excitation wavelength is studied and fluorescence cross sections are estimated. Agreement between the measured fluorescence data and the literature data for riboflavin is observed.

Fluorescence cross sections of bioaerosols and suspended biological agents

Laser-induced fluorescence is used to investigate fluorescence properties of unwashed Bacillus thuringiensis and Bacillus subtilis spores, ovalbumin, and washed bacteriophage MS2. A fluorescence detector is calibrated to obtain absolute fluorescence cross sections. Fluorescence maps of biological aerosols and suspensions are measured at a wide excitation range from 210 to 419 nm and a wide detection range from 315 to 650 nm. The dominant features of the measured spectra are the amino acid peaks, having excitation maxima at 220 and 280 nm. The peaks are similar for the bacterial spores, both for aerosols and suspensions, whereas the peaks are shifted toward the shorter emission wavelengths for the suspended ovalbumin and MS2. Moreover, the fluorescence emission, excited above 320 nm is more intensive for the aerosols than the suspensions.

Wavelength modulation waveforms in laser photoacoustic spectroscopy

Different wavelength modulation waveforms were studied comprehensively in tunable diode laser photoacoustic spectroscopy. The generation of the photoacoustic signal was studied by way of simulations and experiments. A cantilever-enhanced photoacoustic detector and CO(2) sample gas were used in the experiments. The modulation waveforms compared in this study were sinusoidal, triangular, shaped, and quasi-square waves. All four waveforms allow background-free detection of trace gases. Compared to the conventionally used sinusoidal modulation, the triangular, shaped, and quasi-square waves enhanced the photoacoustic signal by factors of 1.12, 1.42, and 1.57, respectively.

Long distance active hyperspectral sensing using high-power near-infrared supercontinuum light source.

A hyperspectral remote sensing instrument employing a novel near-infrared supercontinuum light source has been developed for active illumination and identification of targets. The supercontinuum is generated in a standard normal dispersion multi-mode fiber and has 16 W total optical output power covering 1000 nm to 2300 nm spectral range. A commercial 256-channel infrared spectrometer was used for broadband infrared detection. The feasibility of the presented hyperspectral measurement approach was investigated both indoors and in the field. Reflection spectra from several diffusive targets were successfully measured and a measurement range of 1.5 km was demonstrated.

Resonant photoacoustic cell for pulsed laser analysis of gases at high temperature

A new approach to high temperature gas analysis by means of photoacoustic (PA) spectroscopy is presented. The transverse modes of the resonant PA cell were excited with a pulsed laser and detected with a microphone. Changes in the properties of the PA cell resulting from a varying temperature are discussed and considered when processing the PA signal. The feasibility of the proposed method was demonstrated by studying PA response from saturated vapor of potassium chloride (KCl) in the temperature range extending from 410 to 691 degrees C. The PA spectrum, the detection limit, and the signal saturation of KCl vapor are discussed. At 245 nm excitation wavelength and 300 microJ pulse energy, the achieved detection limit for KCl is 15 ppb.

Towards direct closure of the quantum metrological triangle

In this paper, plans and progress of a Finnish collaboration towards direct closure of the quantum metro- logical triangle are presented. The experimental concept and the present status of the main components, including two possibilities of the single charge transport device, Bloch oscillating transistor (BOT) based null detector, and a thin-film cryoresistor, are described.

Development of the sinis turnstile for the quantum metrological triangle

We develop a quantum current standard based on the hybrid superconductor-insulator-normal-metal-insulator-superconductor (SINIS) structure in turnstile operation. We discuss the properties of the device and the relevant error sources. We also present a preliminary plan how to implement the device in a direct quantum metrological triangle experiment.

Transversely Excited Multipass Photoacoustic Cell Using Electromechanical Film as Microphone

A novel multipass photoacoustic cell with five stacked electromechanical films as a microphone has been constructed, tested and characterized. The photoacoustic cell is an open rectangular structure with two steel plates facing each other. The longitudinal acoustic resonances are excited transversely in an optical multipass configuration. A detection limit of 22 ppb (10−9) was achieved for flowing NO2 in N2 at normal pressure by using the maximum of 70 laser beams between the resonator plates. The corresponding minimum detectable absorption and the normalized noise-equivalent absorption coefficients were 2.2 × 10−7 cm−1 and 3.2 × 10−9 cm−1WHz−1/2, respectively.