Evanescent-wave photoacoustic spectroscopy with optical micro/nano fibers

We demonstrate gas detection based on evanescent-wave photoacoustic (PA) spectroscopy with tapered optical fibers. Evanescent-field instead of open-path absorption is exploited for PA generation, and a quartz tuning fork is used for PA detection. A tapered optical fiber with a diameter down to the wavelength scale demonstrates detection sensitivity similar to an open-path system but with the advantages of easier optical alignment, smaller insertion loss, and multiplexing capability.     

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     

Sensitive wavelength-modulated photoacoustic spectroscopy with a pulsed optical parametric oscillator

With a laser-excited acoustic wave as the carrier wave and by modulation of the light wavelength of a multikilohertz-repetition-rate optical parametric oscillator at a lower frequency than the acoustic frequency, we demonstrate a wavelength-amplitude double-modulation technique and achieve an enhancement factor of 35 in sensitivity in photoacoustic trace gas detection with the technique.     

On-line monitoring of Au nanoparticles formation by optical spectroscopy

X-Ray Magnetic Circular Dichroism experiments have been conducted on a vanadium inorganic salt and a vanadium enamino-ketone complex. Measurements at the K edge of oxygen and nitrogen reveal the amount of magnetic moment transferred in the 2p orbitals of the ligand atoms from the magnetic V ion. Measurements at the L edge of vanadium show that the orbital moment is small and that J = L + S, contrary to the expected J = L-S coupling for a 3d metal with less than five d-electrons. This surprising inobservance of Hunds third rule emphasizes the need for more detailed studies and calculations on such hybrid molecules.Received: 19 November 2003, Published online: 20 April 2004PACS: 75.20.-g Diamagnetism, paramagnetism, and superparamagnetism - 75.70.Ak Magnetic properties of monolayers and thin films - 78.70.Dm X-ray absorption spectra     

Detection of N2O by photoacoustic spectroscopy with a compact, pulsed optical parametric oscillator

A pulsed optical parametric oscillator (OPO) operated in an optical cavity with a grazing-incidence grating configuration (GIOPO) was used for sensitive photoacoustic detection of trace quantities of dinitrogen oxide (N₂O). The (ν₁+ν₃) combination vibration band of N₂O was excited with the idler beam of the GIOPO at 2.86 μm using an optical cavity optimized for the idler beam. The linewidth of the GIOPO could be reduced to 0.4 cm^-1, allowing the rotational structure of the absorption spectrum to be resolved. A concentration sensitivity (signal-to-noise ratio=3) of 60 parts in 10⁹ by volume (60 ppb V) N₂O in synthetic air was obtained. This may be sufficient for continuous monitoring of N₂O in the atmosphere. Received: 29 April 2002 / Revised version: 4 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +49-6221/54-4255, E-mail: peter.hess@urz.uni-heidelberg.de     

Fluorescence spectroscopy of polynuclear aromatic compounds in environmental monitoring

The occurrence of polynuclear aromatic compounds (PAC) in the environment and experimental techniques suitable for the detection of PAC in environmental compartments are briefly reviewed. The specific requirements for on-site andin situ environmental analysis are outlined. Particular emphasis is given to fluorescence spectroscopic techniques for the investigation of humic acid- and soil-containing samples. Some examples of studies in the literature on Shpol'skii and jet spectroscopy and on laser-induced fluorescence (OF) measurements of PAC and mineral oils are highlighted. Contaminants in the environment are usually encountered as multicomponent mixtures in very complex matrices. Total fluorescence analysis in combination with the chemometrical technique of rank annihilation factor analysis (RAFA) was employed for the evaluation of a six-component PAC mixture in toluene. It was shown that even in the presence of strong spectral overlap the qualitative identification of all compounds and the reliable quantification of five substances was possible. Results are presented from our stationary and time-resolved fluorescence investigations of the interactions between pyrene and humic acid in water. The Stern-Volmer analysis showed a significant effect of pH on the static quenching efficiency which can be explained by the pH-dependent macromolecular structure of humic acids. Preliminary results from studies of the deactivation of triplet PAC and quenching of delayed fluorescence by humic acid are reported. LIF measurements of mineral oils directly from soil surfaces and of a model oil in a soil column were performed with a fiber-optic coupled multichannel spectrometer. The fluorescence intensity/ concentration relationships were established for a crude and a fuel oil; the corresponding lower limits of detection (LOD) were determined to be 0.025 and 0.125% m/m (mass/mass percentages). These detection limits are compared with realistic oil contaminations of soils. In a soil column designed to mimic fixed-bed bioreactors the distributions of fluorescence signal intensities from a perylene-doped model oil before and after water flooding were determined. These results fromin situ measurements can provide a quantitative basis for the modelling of temporal and spatial contaminants' distributions in reactor design.     

Oxidation-state-specific detection of uranium in aqueous solution by photoacoustic spectroscopy

By means of photoacoustic spectroscopy it has been possible to detect U(IV) and U(VI) in aqueous solution in the 10^?6 M/L range. Piezoelectric transducer detection, pulsed laser radiation and a differential method to reduce solvent and window absorption has been used. Photoacoustic spectroscopy seems to be a suitable method for the low level detection of actinide elements.     

Thermal and optical properties of Cd2SnO4 thin films using photoacoustic spectroscopy

Cadmium stannate (Cd₂SnO₄) thin films were prepared by the RF magnetron sputtering technique on glass substrates with substrate temperatures of room temperature (RT), 100°C, 200°C and 300°C. Photoacoustic analyses were made to obtain the thermal diffusivity and the optical bandgap values of the Cd₂SnO₄ thin films. The change in thermal diffusivity of the films with the substrate temperature was analyzed. The optical bandgap values obtained from the photoacoustic spectroscopy were compared with the values obtained from the optical transmittance spectra. X-ray photoelectron spectroscopic (XPS) studies confirm the formation of stoichiometric films. Surface morphological studies by atomic force microscopy (AFM) revealed the crystalline nature of the films deposited at 100°C.     

Determination of phase transitions in binary systems of mesogenic compounds by optical absorption spectroscopy

The use is described of absorption spectroscopy for determining phase transitions in the mesogenic compound cholesteryl myristate (CM) and in binary mixtures of terephthalbis-butyl-aniline (TBBA) and cholesteryl myristate. The temperature dependence of the optical densities in the visible region at phase transitions is reported. The transition temperatures obtained with this method are in good agreement with the results obtained with other methods.     

Study of nanodispersed aluminum and iron alcosols by photoacoustic spectroscopy

Nanodispersed aluminum and iron alcosols were prepared by ultrasonic dispersion of nanodispersed aluminum and iron powders in absolute ethanol. The photoacoustic signal (PAS) produced in modulated CO₂ laser irradiation (1.026 and 1.096 kHz) of alcosols depends on the nature and method of nanoparticle fabrication and does not depend on their concentration in ethanol (within 1-5 g/l). Chemical interaction between metal nanoparticles and ethanol activated by laser irradiation or/and ultrasound is considered as the cause of the PAS.     

钕配合物宽波段光声光谱研究

利用紫外－可见、近红外及中红外光声光谱对钕配合物的激发态能级状况、驰豫过程,荧光性质进行探讨,并深入研究了钕离子和配体对彼此光声谱峰移动和峰强度的影响。     

光学玻璃渐进多焦点镜片的制法工艺研究

为满足特殊的成像要求,渐进多焦点镜片表面需要使用非旋转对称非球面,采用传统的加工方法很难实现。通过对该产品制法核心关键技术进行探讨,提出了一种新型的渐进多焦点镜片的制备工艺——下沉成型法。该技术可对光学玻璃双焦镜片进行升级,有利于促进光学玻璃在眼镜业的发展。     

Analysis of liquid surface films by pulsed laser photoacoustic spectroscopy

The photoacoustic generation of plane acoustic waves in strongly absorbing or opaque liquids by pulsed laser radiation is discussed both experimentally and theoretically. The regimes of a confined and a free surface of the liquid are considered. The model which takes the temporal shape of the laser pulses applied in the experiments into account, implies that spectroscopic studies are feasible with direct photoacoustic generation and detection also for opaque liquids. The experiments are performed with a tunable hybrid CO₂ laser and piezoelectric detection. For the first time liquid/liquid interfaces are studied by this technique. We demonstrate that the presence of an absorbing liquid film with a thickness of >1 m on the surface of another liquid amplifies the acoustic signal which is detected in the bottom liquid. The enhancement depends on the thickness and the optical and thermal properties of the film medium. The surface layer can be analyzed on the basis of the photoacoustic spectrum. It is also shown that this non-contact method is surface-film selective and should thus prove useful for pollution analysis of liquid surfaces.     

Optical properties of xenon implanted CuInSe2 by photoacoustic spectroscopy

A theoretical relation is derived for the normalized photoacoustic amplitude signal of a gas-coupled cell for the case of double-layer solid samples with particular application given to ion implanted semiconductors. Numerical estimates for a solar cell of the type CdS/CuInSe₂ based on experimental measured data of these compounds are given to illustrate the photoacoustic effect originating from double-layer samples. In application to ion implanted semiconductors, we show that the absorption coefficient of the implanted layer can be very easily extracted by photoacoustic spectroscopy if the absorption coefficient of the untreated substrate is known. We also present the optical properties results obtained from the analysis of the effect of xenon implantation into CuInSe₂ single crystals with the energy of 40 keV and a dose of 5×10¹⁶ ions/cm².     

Gas monitoring in the process industry using diode laser spectroscopy

2 , CO, NH₃, HCl and HF are described together with measurements from several installations. The monitors show continuous measurements with fast response and good sensitivity, all of which is difficult to obtain with conventional techniques such as wet chemical analysis. Received: 19 March 1998/Revised version: 2 June 1998     

Quantitative high-resolution on-line NMR spectroscopy in reaction and process monitoring

On-line nuclear magnetic resonance spectroscopy (on-line NMR) is a powerful technique for reaction and process monitoring. Different set-ups for direct coupling of reaction and separation equipment with on-line NMR spectroscopy are described. NMR spectroscopy can be used to obtain both qualitative and quantitative information from complex reacting multicomponent mixtures for equilibrium or reaction kinetic studies. Commercial NMR probes can be used at pressures up to 35 MPa and temperatures up to 400 K. Applications are presented for studies of equilibria and kinetics of complex formaldehyde-containing mixtures as well as homogeneously and heterogeneously catalyzed esterification kinetics. Direct coupling of a thin-film evaporator is described as an example for the benefits of on-line NMR spectroscopy in process monitoring.     

Speciation of actinide ions in aqueous solution by laser-induced pulsed photoacoustic spectroscopy

The oxidation-state specific detection of actinide ions, U(VI), Pu(IV), Pu(VI), and Am(III), was investigated by pulsed laser photoacoustic spectroscopy. With a single-beam differential technique, the solvent effect is compensated and thus the detection sensitivity substantially increased. The observed detection sensitivities are8×10^–7M/L for U(VI)7×10^–8M/L for Pu(IV)3×10^–8M/L for PU(VI)2×10^–8M/L for Am(III)The present method facilitates the study of complexation and polymerization of actinide ions in the submicromole concentration range.     

Detection of soybean rust contamination in soy leaves by FTIR photoacoustic spectroscopy

In this work the Photoacoustic Infrared Spectroscopy from 4000 to 400 cm^-1 was applied, by the first time to our knowledge, to diagnostic the soy bean rust or Asian rust contamination on soy leafs caused by the fungi Phakopsora pachyrhizi. The obtained results shown that a premature, fast and precise diagnosis can be achieved using this technique before it can be detect by the conventional visual method. The early identification of the fungi infection avoid massive lost in the soy production and decrease the intense use of fungicide whose is necessary when the infection is in advanced stagy.     

Infrared photoacoustic spectroscopy in catalysis and surface science

The analysis of solid samples can often be a difficult problem for the researchers dealing with infrared (IR) spectroscopy. In conventional absorption spectroscopy the measurement of absorption is transferred to that of the radiation transmitted through the sample. Three methods stand out as being more suitable for studying solid materials. These methods are: diffuse reflectance (DR), photoacoustic spectroscopy (PAS), and Fourier transform (FT) Raman. All three methods require little or no sample preparation, and therefore are ideal for the samples that may change during the preparation as mineral oil mulls or KBr disks. In the case of PAS, the adsorbed radiation is determined directly via its heat and hence the sound produced in the sample. Fourier transform infrared PAS (FT-IR/PAS) is one of the main IR techniques which can be successfully applied in catalysis and surface science research. Recent examples of this spectroscopic technique application will be presented.