Environmental Monitoring - using diode-laser-based spectroscopic techniques

Monitoring of environmental gases is necessary to understand the complex processes governing global warming and the impact of pollutant emissions related to human activity. Diode-laser-based spectroscopic techniques, being robust and affordable, have a great potential to become an industrially well-established technology for environmental sensing. This thesis deals with the further development of these techniques, demonstrated in several applications to atmospheric gas detection and sensing. The accessible spectral range of tunable diode lasers was extended by use of sum-frequency generation. High-resolution ultraviolet spectroscopy of mercury isotopes around 254 nm was performed on low-pressure cells as well as at atmospheric pressure. Ultraviolet radiation around 300 nm, utilized for monitoring of sulfur dioxide and studies of the pressure dependence of the absorption spectrum, was produced using a sum-frequency generation scheme employing a blue and a near-infrared diode laser. Detection sensitivity was improved by several orders of magnitude by employing frequency modulation techniques. This was demonstrated with blue continuous-wave diode lasers in measurements on ground state potassium atoms, and lead atoms in very weakly populated meta-stable states. In the red spectral region, traffic-generated emission of nitrogen dioxide was monitored in situ using long path absorption at a wavelength around 635 nm. A new temporal gas-correlation scheme was developed, which overcomes the intrinsic multimode and mode-jump behaviour of diode lasers. The concentration of a gas under study is determined by temperature tuning the wavelength of a diode laser across an absorption band of the gas, and by simultaneous temporal correlation of the detected signal with the signal from a known reference gas concentration. No knowledge of the exact spectrum is needed. The method was tested in diffusion related measurements. A novel technique for analysis of free gas in scattering media by use of absorption spectroscopy, GASMAS, was introduced. The sharp absorption features of the gas, contrasted to the very slow wavelength dependence of the bulk material, can be picked up by use of modulation techniques. Dispersed molecular oxygen embedded in various natural and man-made porous materials was detected and measured. The gas concentration was determined by combining absorption and time-resolved laser spectroscopy measurements. Investigations were performed to assess the internal gas pressure and gas diffusion characteristics. A new single-aerosol particle detector using a coupled-cavity diode laser was developed. Simultaneous size and shape determination was demonstrated by recording of the optical extinction and a diffraction image in the near-forward scattered light

Combined optical porosimetry and gas absorption spectroscopy in gas-filled porous media using diode-laser-based frequency domain photon migration

A combination method of frequency domain photon migration (FDPM) and gas in scattering media absorption spectroscopy (GASMAS) is used for assessment of the mean optical path length (MOPL) and the gas absorption in gas-filled porous media, respectively. Polystyrene (PS) foams, with extremely high physical porosity, are utilized as sample materials for proof-of-principle demonstration. The optical porosity, defined as the ratio between the path length through the pores and the path length through the medium, is evaluated in PS foam and found consistent with the measured physical porosity. The method was also utilized for the study of balsa and spruce wood samples. (C) 2012 Optical Society of Americ

Frequency-modulation spectroscopy with blue diode lasers

Frequency-modulation spectroscopy provides ultrasensitive absorption measurements. The technique is especially adaptable to diode lasers, which can be modulated easily, and has been used extensively in the near-infrared and infrared spectral regions. The availability of blue diode lasers now means that the accessible wavelength region can be increased. We successfully demonstrate wavelength-modulation spectroscopy and two-tone frequency-modulation spectroscopy for the weak second resonance line of potassium at 404.8 nm and for the transition at 405.8 nm in lead, starting from the thermally populated 6p(2) P-3(2) metastable level, information on the modulation parameters is obtained with a fitting procedure. Experimental signal-to-noise ratios: at different absorption levels are compared with theoretical signal-to-noise ratios and show good agreement. Detection sensitivities of 2 x 10(-6) and 5 x 10(-6) for wavelength and two-tone frequency-modulation spectroscopy, respectively, for a 120-Hz bandwidth are demonstrated. (C) 2000 Optical Society of America

Long-path monitoring of NO2 with a 635 nm diode laser using frequency-modulation spectroscopy

In situ monitoring of traffic-generated nitrogen dioxide (NO2) emissions using long-path absorption spectroscopy is reported. High-sensitivity detection of NO2 is achieved by employing two-tone frequencymodulation spectroscopy at a visible absorption band using a tunable high-power diode laser operated around 635 nm. A real-time absorption spectrometer is accomplished by repetitively applying a rectangular current pulse to the diode-laser operating current, allowing detection of isolated NO2 absorption lines. A detection limit of 10 mu g/m(3) for NO2 at atmospheric pressure using a 160 m absorption path is demonstrated. Continuous monitoring of NO2 over a road intersection at peak traffic is performed

Gas spectroscopy and optical path-length assessment in scattering media using a frequency-modulated continuous-wave diode laser

Simultaneous assessment of the spectroscopic absorption signal of gas enclosed in a scattering medium and the corresponding optical path length of the probing light is demonstrated using a single setup. Sensitive gas absorption measurements are performed by a tunable diode laser using wavelength-modulation spectroscopy, while the path length is evaluated by the frequency-modulated cw technique commonly used in the field of telecommunication. Proof-of-principle measurements are demonstrated with water vapor as the absorbing gas and using polystyrene foam as an inhomogeneously scattering medium. The combination of these techniques opens up new possibilities for straightforward evaluation of gas presence and exchange in scattering media. (C) 2011 Optical Society of Americ

Analysis of gas dispersed in scattering media

Monitoring of free gas embedded in scattering media, such as wood, fruits, and synthetic materials, is demonstrated by use of diode laser spectroscopy combined with sensitive modulation techniques. Gas detection is made possible by the contrast of the narrow absorptive feature of the free-gas molecules with the slow wavelength dependence of the absorption and scattering cross sections in solids and liquids. An absorption sensitivity of 2.5 x 10(-4), corresponding to a 1.25-mm air column, is demonstrated by measurements of dispersed molecular oxygen. These techniques open up new possibilities for characterization and diagnostics, including internal gas pressure and gas-exchange assessment, in organic and synthetic materials. (C) 2001 Optical Society of America. OCIS codes: 300.6360, 290.7050, 290.5820, 170.3660, 020.3690, 160.4890

Temporal correlation scheme for spectroscopic gas analysis using multimode diode lasers

The reliability of diode lasers used in spectroscopic applications is limited by their intrinsic multimode and mode-jump behavior when wavelength-tuned by current or temperature. We report on a scheme for gas analysis based on temporal correlation between absorption signals from an unknown external and a known reference gas concentration, simultaneously recorded when the diode laser wavelength is temperature-tuned across absorption features of the gas of interest. This procedure, which does not require any knowledge of the exact spectrum, also eliminates light intensity fluctuations due to mode competition. The method is illustrated for atmospheric oxygen absorption applied to diffusion measurements

Concentration measurement of gas embedded in scattering media by employing absorption and time-resolved laser spectroscopy

Diode-laser-based absorption spectroscopy for the evaluation of embedded gas concentrations in porous materials is demonstrated in measurements of molecular oxygen dispersed throughout scattering polystyrene foam, used here as a generic test material. The mean path length of light scattered in the material is determined with the temporal characteristics of the radiation transmitted through the sample. This combined with sensitive gas-absorption measurements employing wavelength-modulation spectroscopy yields an oxygen concentration in polystyrene foam of 20.4% corresponding to a foam porosity of 98%, which is consistent with manufacturing specifications. This feasibility study opens many possibilities for quantitative measurements by using the method of gas-in-scattering-media absorption spectroscopy. (C) 2002 Optical Society of America

Autofluorescence insensitive imaging using upconverting nanocrystals in scattering media

Autofluorescence is a nuisance in the field of fluorescence imaging and tomography of exogenous molecular markers in tissue, degrading the quality of the collected data. In this letter, we report autofluorescence insensitive imaging using highly efficient upconverting nanocrystals (NaYF4: Yb3+ /Tm3+) in a tissue phantom illuminated with near- infrared radiation of 85 mW/cm(2). It was found that imaging with such nanocrystals leads to an exceptionally high contrast compared to traditional downconverting fluorophores due to the absence of autofluorescence. Upconverting nanocrystals may be envisaged as important biological markers for tissue imaging purposes. c 2008 American Institute of Physics. [DOI: 10.1063/1.3005588