Acousto-optic differential optical absorption spectroscopy for atmospheric measurement of nitrogen dioxide in Hong Kong

Measurement of the atmospheric concentration of nitrogen dioxide (NO(2)) pollutant was demonstrated by differential optical absorption spectroscopy (DOAS) using a visible acousto-optic tunable filter. In a traditional spectral scanning DOAS system for atmospheric concentration monitoring, a highly stable light source is required. When the light intensity fluctuates during scanning, the concentration retrieval will be inaccurate. In order to reduce the error due to intensity fluctuations, a modified DOAS system has been developed by introducing a broadband light intensity monitoring channel. Using the measured intensity of the broadband channel as the intensity of the light source, the spectrum can be de-biased and the residual intensity variation will primarily result from atmospheric extinction. In addition, by employing the lock-in detection technique, the background light interference is also removed in the modified DOAS system. The atmospheric NO(2) concentration measurement was performed at the campus of City University of Hong Kong, and the results were compared with the concentration reported from a nearby monitoring station in Sham Shui Po, operated by the Hong Kong Environmental Protection Department.     

Time-resolved diffuse optical spectroscopy: a differential absorption approach

A method is presented for the estimate of spectral changes in the absorption properties of turbid media from time-resolved diffuse optical spectroscopy. The method relies on the hypothesis of constant scattering over the wavelength range of interest, but no limitations come from the sample size and shape as the method is derived directly from the Beer-Lambert law. The effects of a moderate spectral dependence of the scattering properties and of the non-ideal instrument response function were investigated theoretically, and the results were confirmed experimentally, showing that the method can be profitably applied in cases of practical interest.     

Differential optical absorption spectroscopy system used for atmospheric mercury monitoring

A high-resolution differential optical absorption spectroscopy (DOAS) system for long-path atmospheric pollution monitoring is described. The system, consisting of a broadband lamp and a dispersive, fast-scanning optical receiver, separated by a few kilometers, was used in measurements of different pollutants, highlighted by the monitoring of the local concentration of atomic mercury. Mercury levels in the ppt (1:10(12)) range were assessed by comparisons with laboratory measurements.     

Operator representation as a new differential optical absorption spectroscopy formalism

UV-visible absorption spectroscopy with extraterrestrial light sources is a widely used technique for the measurement of stratospheric and tropospheric trace gases. We focus on differential optical absorption spectroscopy (DOAS) and present an operator notation as a new formalism to describe the different processes in the atmosphere and the simplifying assumptions that compose the advantage of DOAS. This formalism provides tools to classify and reduce possible error sources of DOAS applications.     

Improvement of differential optical absorption spectroscopy with a multichannel scanning technique

Differential optical absorption spectroscopy (DOAS) of atmospheric trace gases requires the detection of optical densities below 0.1%. Photodiode arrays are used more and more as detectors for DOAS because they allow one to record larger spectral intervals simultaneously. This type of optical multichannel analyzer (OMA), however, shows sensitivity differences among the individual photodiodes (pixels), which are of the order of 1%. To correct for this a sensitivity reference spectrum is usually recorded separately from the trace-gas measurements. Because of atmospheric turbulence the illumination of the detector while an atmospheric absorption spectrum is being recorded is different from the conditions during the reference measurement. As a result the sensitivity patterns do not exactly match, and the corrected spectra still show a residual structure that is due to the sensitivity difference. This effect usually limits the detection of optical densities to approximately 3 × 10(-4). A new method for the removal of the sensitivity pattern is presented in this paper: Scanning the spectrometer by small wavelength increments after each readout of the OMA allows one to separate the OMA-fixed pattern and the wavelength-fixed structures (absorption lines). The properties of the new method and its applicability are demonstrated with simulated spectra. Finally, first atmospheric measurements with a laser long-path instrument demonstrate a detection limit of 3 × 10(-5) of a DOAS experiment.     

Improving long-path differential optical absorption spectroscopy with a quartz-fiber mode mixer

Long-path differential optical absorption spectroscopy (DOAS) has become an increasingly important method for determination of the concentration of tropospheric trace gases (e.g., O(3), NO(2), BrO, ClO). The use of photodiode array (PDA) detectors enhances long-path DOAS systems considerably owing to PDA's higher sensitivity resulting from the multiplex advantage. The detection limits of these systems are expected to be 1 order of magnitude lower than systems of similar optical setup with scanning detectors. When the scanning detector is simply replaced by a PDA, unwanted spectral structures of as much as 8 x 10(-3) appear. The size of these randomly changing structures exceeds the photon noise level by 2-3 orders of magnitude thus severely limiting the sensitivity. We show that an angular dependence of the response of the PDA causes this structure in combination with unavoidable changes in the illumination. A quartz-fiber mode mixer, which makes the illumination of the spectrograph-detector system nearly independent of the angular intensity distribution of the measured light, was developed and tested. This new device reduces the unwanted structures in laboratory and field experiments by a factor of 10. The detection limits of long-path DOAS instruments with PDA detectors are improved by the same amount and are thus lower than those of currently used systems with scanning detectors. At the same time a much shorter measurement time (by ~1 order of magnitude) becomes possible.     

Design of differential optical absorption spectroscopy long-path telescopes based on fiber optics

We present a new design principle of telescopes for use in the spectral investigation of the atmosphere and the detection of atmospheric trace gases with the long-path differential optical absorption spectroscopy (DOAS) technique. A combination of emitting and receiving fibers in a single bundle replaces the commonly used coaxial-Newton-type combination of receiving and transmitting telescope. This very simplified setup offers a higher light throughput and simpler adjustment and allows smaller instruments, which are easier to handle and more portable. The higher transmittance was verified by ray-tracing calculations, which result in a theoretical factor threefold improvement in signal intensity compared with the old setup. In practice, due to the easier alignment and higher stability, up to factor of 10 higher signal intensities were found. In addition, the use of a fiber optic light source provides a better spectral characterization of the light source, which results in a lower detection limit for trace gases studied with this instrument. This new design will greatly enhance the usability and the range of applications of active DOAS instruments.     

Alternative method for concentration retrieval in differential optical absorption spectroscopy atmospheric-gas pollutant measurements

Differential optical absorption spectroscopy is a widely used technique for open-column atmospheric-gas pollution monitoring. The concentration retrieval is based on the fitting of the measured differential absorbance through the Lambert-Beer law. We present an alternative method for calculating the gas concentration on the basis of the proportionality between differential absorbance and differential absorption cross section of the gas under study. The method can be used on its own for single-component analysis or as a complement to the standard technique in multicomponent cases. The performance of the method for the case of cross interference between two gases is analyzed. The procedure can be used with differential absorption cross sections measured in the laboratory or taken from the literature. In addition, the method provides a criterion to discriminate against different species having absorption features in the same wavelength range.     

Ground-based differential absorption lidar for water-vapor and temperature profiling: methodology

A comprehensive formulation of the differential absorption lidar (DIAL) methodology is presented that explicitly includes details of the spectral distributions of both the transmitted and the backscattered light. The method is important for high-accuracy water-vapor retrievals and in particular for temperature measurements. Probability estimates of the error that is due to Doppler-broadened Rayleigh scattering based on an extended experimental data set are presented, as is an analytical treatment of errors that are due to averaging in the nonlinear retrieval scheme. System performance requirements are derived that show that water-vapor retrievals with an accuracy of better than 5% and temperature retrievals with an accuracy of better than 1 K in the entire troposphere are feasible if the error that results from Rayleigh-Doppler correction can be avoided. A modification of the DIAL technique, high-spectral-resolution DIAL avoids errors that are due to Doppler-broadened Rayleigh backscatter and permits simultaneous water-vapor and wind measurements with the same system.     

Concurrent multiaxis differential optical absorption spectroscopy system for the measurement of tropospheric nitrogen dioxide

The development of a new concurrent multiaxis (CMAX) sky viewing spectrometer to monitor rapidly changing urban concentrations of nitrogen dioxide is detailed. The CMAX differential optical absorption spectroscopy (DOAS) technique involves simultaneous spectral imaging of the zenith and off-axis measurements of spatially resolved scattered sunlight. Trace-gas amounts are retrieved from the measured spectra using the established DOAS technique. The potential of the CMAX DOAS technique to derive information on rapidly changing concentrations and the spatial distribution of NO2 in an urban environment is demonstrated. Three example data sets are presented from measurements during 2004 of tropospheric NO2 over Leicester, UK (52.62 degrees N, 1.12 degrees W). The data demonstrate the current capabilities and future potential of the CMAX DOAS method in terms of the ability to measure real-time spatially disaggregated urban NO2.     

Applicability of light-emitting diodes as light sources for active differential optical absorption spectroscopy measurements

We present what is to our knowledge the first use of light-emitting diodes (LEDs) as light sources for long-path differential optical absorption spectroscopy (LP-DOAS) measurements of trace gases in the open atmosphere. Modern LEDs represent a potentially advantageous alternative to thermal light sources, in particular to xenon arc lamps, which are the most common active DOAS light sources. The radiative properties of a variety of LEDs were characterized, and parameters such as spectral shape, spectral range, spectral stability, and ways in which they can be influenced by environmental factors were analyzed. The spectra of several LEDs were found to contain Fabry-Perot etalon-induced spectral structures that interfered with the DOAS evaluation, in particular when a constant temperature was not maintained. It was shown that LEDs can be used successfully as light sources in active DOAS experiments that measure NO2 and NO3 near 450 and 630 nm, respectively. Average detection limits of 0.3 parts in 10(9) and 16 parts in 10(12) respectively, were obtained by use of a 6 km light path in the open atmosphere.     

Development of Fourier transform spectrometry for UV-visible differential optical absorption spectroscopy measurements of tropospheric minor constituents

Concentration measurements of trace gases in the atmosphere require the use of highly sensitive and precise techniques. The UV-visible differential optical absorption spectroscopy technique is one that is heavily used for tropospheric measurements. To assess the advantages and drawbacks of using a Fourier transform spectrometer, we built a differential optical absorption spectroscopy optical setup based on a Bruker IFS 120M spectrometer. The characteristics and the capabilities of this setup have been studied and compared with those of the more conventional grating-based instruments. Two of the main advantages of the Fourier transform spectrometer are (1) the existence of a reproducible and precise wave-number scale, which greatly simplifies the algorithms used to analyze the atmospheric spectra, and (2) the possibility of recording large spectral regions at relatively high resolution, enabling the simultaneous detection of numerous chemical species with better discriminating properties. The main drawback, on the other hand, is due to the fact that a Fourier transform spectrometer is a scanning device for which the scanning time is small compared with the total measurement time. It does not have the signal integration capabilities of the CCD or photodiode array-based grating spectrographs. The Fourier transform spectrometer therefore needs fairly large amounts of light and is limited to short to medium absorption path lengths when working in the UV.     

Demonstration of differential backscatter absorption gas imaging

Backscatter absorption gas imaging (BAGI) is a technique that uses infrared active imaging to generate real-time video imagery of gas plumes. We describe a method that employs imaging at two wavelengths (absorbed and not absorbed by the gas to be detected) to allow wavelength-differential BAGI. From the frames collected at each wavelength, an absorbance image is created that displays the differential absorbance of the atmosphere between the imager and the backscatter surface. This is analogous to a two-dimensional topographic differential absorption lidar or differential optical absorption spectroscopy measurement. Gas plumes are displayed, but the topographic scene image is removed. This allows a more effective display of the plume image, thus ensuring detection under a wide variety of conditions. The instrument used to generate differential BAGI is described. Data generated by the instrument are presented and analyzed to estimate sensitivity.     

Particle extinction measured at ambient conditions with differential optical absorption spectroscopy. 2. Closure study

Spectral particle extinction coefficients of atmospheric aerosols were measured with, to the best of our knowledge, a newly designed differential optical absorption spectroscopy (DOAS) instrument. A closure study was carried out on the basis of optical and microphysical aerosol properties obtained from nephelometer, particle soot/absorption photometer, hygroscopic tandem differential mobility analyzer, twin differential mobility particle sizer, aerodynamic particle sizer, and Berner impactors. The data were collected at the urban site of Leipzig during a period of 10 days in March 2000. The performance test also includes a comparison of the optical properties measured with DOAS to particle optical properties calculated with a Mie-scattering code. The computations take into account dry and ambient particle conditions. Under dry particle conditions the linear regression and the correlation coefficient for particle extinction are 0.95 and 0.90, respectively. At ambient conditions these parameters are 0.89 and 0.97, respectively. An inversion algorithm was used to retrieve microphysical particle properties from the extinction coefficients measured with DOAS. We found excellent agreement within the retrieval uncertainties.     

A pulsed optical absorption spectroscopy study of wide band-gap optical materials

The paper presents the results of a study on the formation and evolution of short-lived radiation-induced defects in wide band-gap optical materials with the mobile cations. The spectra and decay kinetics of transient optical absorption (TOA) of radiation defects in crystals of potassium and ammonium dihydro phosphates (KH₂PO₄ and NH₄H₂PO₄) were studied by means of the method of pulsed optical absorption spectroscopy with the nanosecond time resolution under excitation with an electron-beam (250 keV, 10 ns). A model of electron tunneling between the electron and hole centers under conditions of the thermally stimulated mobility of one of the recombination process partners was developed. The model describes all the features of the induced optical density relaxation kinetics observed in nonlinear optical crystals KH₂PO₄ and NH₄H₂PO₄ in a broad decay-time range of 10 ns–10 s after the pulse of radiation exposure. The paper discusses the origin of radiation defects that determine the TOA, as well as the dependence of the decay kinetics of the TOA on the temperature, excitation power and other experimental conditions.     

Numerical analysis and estimation of the statistical error of differential optical absorption spectroscopy measurements with least-squares methods

Differential optical absorption spectroscopy (DOAS) has become a widely used method to measure trace gases in the atmosphere. Their concentration is retrieved by a numerical analysis of the atmospheric absorption spectra, which often are a combination of overlapping absorption structures of several trace gases. A new analysis procedure was developed, modeling atmospheric spectra with the absorption structures of the individual trace gases, to determine their concentrations. The procedure also corrects differences in the wavelength-pixel mapping of these spectra. A new method to estimate the error of the concentrations considers the uncertainty of this correction and the influence of random residual structures in the absorption spectra.     

Multibeam long-path differential optical absorption spectroscopy instrument: a device for simultaneous measurements along multiple light paths

A novel long-path differential optical absorption spectroscopy (DOAS) apparatus for measuring tropospheric trace gases and the first results from its use are presented: We call it the multibeam instrument. It is the first active DOAS device that emits several light beams simultaneously through only one telescope and with only one lamp as a light source, allowing simultaneous measurement along multiple light paths. In contrast to conventional DOAS instruments, several small mirrors are positioned near the lamp, creating multiple virtual light sources that emit one light beam each in one specific direction. The possibility of error due to scattering between the light beams is negligible. The trace-gas detection limits of NO2, SO2, O3, and H2CO are similar to those of the traditional long-path DOAS instrument.     

Picosecond pump-probe absorption spectroscopy in gases: models and experimental validation

Picosecond pump-probe absorption spectroscopy is a spatially resolved technique that is capable of measuring species concentrations in an absolute sense without the need for calibrations. When laser pulses are used that are shorter than the collision time in a sample, this pump-probe technique exhibits reduced sensitivity to collisional effects such as electronic quenching. We describe modeling and experimental characterization of this technique. The model is developed from rate equations that describe the interactions of the pump and probe pulses with the sample. Calculations based on the density-matrix equations are used to identify limits of applicability for the model. Excellent agreement between the model and the experimental data is observed when both 1.3- and 65-ps pulses are used to detect potassium in a flame and in an atomic vapor cell.     

Sum-frequency-generation system for differential absorption lidar measurement of atmospheric nitrogen dioxide

A sum-frequency-generation system for differential absorption lidar measurement of atmospheric nitrogen dioxide in the lower troposphere was developed. The system uses a combination of a pair of KD*P crystals and a tunable dye laser with LDS 765 dye pumped by the second harmonic of a Nd:YAG laser to generate lambdaon and lambdaoff alternatively. Compared with the conventional system that uses Coumarin 445 dye pumped by the third harmonic, the output energy and long-term stability were improved. By use of this system, atmospheric NO2 concentrations of approximately 10-50 ppb were measured, with an instrumental error of approximately 7 ppb.